U.S. patent number 4,080,491 [Application Number 05/714,833] was granted by the patent office on 1978-03-21 for process of producing ring-opening polymerization products.
This patent grant is currently assigned to Showa Denko K.K.. Invention is credited to Shoichi Kobayashi, Yukio Kobayashi, Takashi Ueshima.
United States Patent |
4,080,491 |
Kobayashi , et al. |
March 21, 1978 |
**Please see images for:
( Certificate of Correction ) ** |
Process of producing ring-opening polymerization products
Abstract
A process of producing a ring-opening polymerization product of
a norbornene derivative containing at least one polar group or
aromatic group, a norbornadiene derivative containing at least one
of said groups or a cycloolefin using a catalyst system prepared
from an organometallic compound and the reaction product of
tungsten oxide or molybdenum oxide and a phosphorus pentahalide or
phosphorus oxytrihalide or these compounds and other third
components. The catalyst system possesses a high polymerization
activity.
Inventors: |
Kobayashi; Yukio (Yokohama,
JA), Ueshima; Takashi (Yokohama, JA),
Kobayashi; Shoichi (Yokohama, JA) |
Assignee: |
Showa Denko K.K. (Tokyo,
JA)
|
Family
ID: |
27561336 |
Appl.
No.: |
05/714,833 |
Filed: |
August 16, 1976 |
Foreign Application Priority Data
|
|
|
|
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Aug 27, 1975 [JA] |
|
|
50-103060 |
Mar 26, 1976 [JA] |
|
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51-32464 |
Mar 26, 1976 [JA] |
|
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51-32465 |
Apr 5, 1976 [JA] |
|
|
51-37274 |
Apr 27, 1976 [JA] |
|
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51-47268 |
May 25, 1976 [JA] |
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51-59642 |
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Current U.S.
Class: |
526/137; 526/113;
526/114; 526/115; 526/121; 526/122; 526/124.1; 526/124.2; 526/127;
526/128; 526/132; 526/136; 526/169; 526/281; 526/283; 526/308;
526/97; 526/98 |
Current CPC
Class: |
C08G
61/08 (20130101) |
Current International
Class: |
C08G
61/00 (20060101); C08G 61/08 (20060101); C08F
004/78 () |
Field of
Search: |
;526/96,97,98,100,102,104,105,114,169,281,136,137,113 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Michl; Paul R.
Attorney, Agent or Firm: Fitzpatrick, Cella, Harper &
Scinto
Claims
We claim:
1. In the process for producing a ringopening polymerization
product comprising polymerizing a monomer selected from the group
consisting of a norbornene derivative containing at least one polar
group or aromatic group, a norbornadiene derivative containing at
least one of said groups and a cycloolefin, the improvement
comprising polymerizing said monomer in the presence of a catalyst
system prepared from
(A) an organometallic compound containing at least one metal
selected from the group consisting of metals of Groups IA, IIA,
IIB, IIIB, IVA and IVB of the periodic table and
(B) the reaction product of at least one oxide selected from the
group consisting of tungsten oxide and molybdenum oxide and from
0.001 to 100 moles per mole of said oxide of at least one
phosphorus compound selected from the group consisting of
phosphorus pentahalide and phosphorus oxytrihalide; the molar ratio
of the component (A) to the component (B) being 0.1 to 100, and
said catalyst system being present in the ring-opening
polymerization system in an amount of 0.001 - 100 gram atom
calculated as tungsten or molybdenum contained in said catalyst
system per 1,000 moles of said monomer.
2. The process of claim 1 wherein said monomer is a norbornene
derivative containing at least one nitrile group.
3. The process of claim 2 wherein said norbornene derivative is
represented by the formula (I) ##STR24## wherein W.sup.1, X.sup.1,
Y.sup.1, and Z.sup.1, which may be the same or different, each
represents a hydrogen atom, a nitrile group or a hydrocarbon group
selected from the group consisting of an alkyl group having at most
20 carbon atoms, a cycloalkyl group having at most 20 carbon atoms,
an alkenyl group having at most 20 carbon atoms, an aryl group
having at most 20 carbon atoms and said hydrocarbon groups
substituted by a nitrile group, at least one of W.sup.1, X.sup.1,
Y.sup.1, and Z.sup.1 being a nitrile group or said hydrocarbon
group substituted with a nitrile group.
4. The process of claim 3, wherein said norborene derivative is
5-cyano-bicyclo[2,2,1]-heptene-2; 5,5-dicyano-bicyclo
[2,2,1]-heptene-2; 5,6-dicyano-bicyclo [2,2,1]-heptene-2;
5-cyano-5-methyl-bicyclo[2,2,1]-heptene-2;
5-cyano-6-methyl-bicyclo[2,2,1]-heptene-2; or
5-cyanomethyl-bicyclo[2,2,1]-heptene-2.
5. The process of claim 1, wherein said monomer is a norbornene
derivative containing at least one ester group.
6. The process of claim 5, wherein said norbornene derivative is
5-methoxycarbonyl-bicyclo [2,2,1]-heptene-2;
5-ethoxycarbonyl-bicyclo [2,2,1]-heptene-2;
5-butoxycarbonyl-bicyclo[2,2,1]-heptene-2;
5-allyloxy-carbonyl-bicyclo[2,2,1]-heptene-2;
5-methyl-5-methoxycarbonyl-bicyclo[2,2,1]-heptene-2;
5-methoxycarbonyl-6-methoxycarbonyl-methyl-bicyclo[2,2,1]-heptene-2;
5,6-dimethyoxycarbonyl-bicyclo[2,2,1]-heptene-2;
5,6-diethoxycarbonyl-bicyclo[2,2,1]-heptene-2;
5,5-dibutoxycarbonyl-bicyclo[2,2,1]-heptene-2;
5-acetoxymethyl-bicyclo[2,2,1]-heptene-2; 5-propoxymethyl-bicyclo
[2,2,1]-heptene-2 or 5-stearoxymethyl-bicyclo[2,2,1]-heptene-2.
7. The process of claim 1, wherein said monomer is a norbornene
derivative containing at least one ether group.
8. The process of claim 7, wherein said norbornene derivative is
5-methoxymethyl-bicyclo[2,2,1]-heptene-2.
9. The process of claim 1, wherein said monomer is a norbornene
derivative containing at least one halogen atom.
10. The process of claim 9, wherein said norbornene derivative is
5-chloro-bicyclo[2,2,1]-heptene-2;
5-chloro-5-methyl-bicyclo[2,2,1]-heptene-2; 5-
chloro-6-methyl-bicyclo[2,2,1]-heptene-2;
5-chloromethyl-bicyclo[2,2,1]-heptene-2;
5,5-dichlorobicyclo[2,2,1]-heptene-2;
5,6-dichloro-bicyclo[2,2,1]-heptene-2;
5,5-bis(chloromethyl)-bicyclo[2,2,1]-heptene-2; or
5,6-bis(chloromethyl)-bicyclo[2,2,1]-heptene-2.
11. The process of claim 1, wherein said monomer is a norbornene
derivative containing at least one acid anhydride group.
12. The process of claim 11, wherein said norbornene derivative is
3,6-methylene-1,2,3,6-tetrahydro-cis-phthalic anhydride;
5,8-methano-1,2,3,4,4a,5,8,8a-octahydronaphthalene-2,3,-dicarboxylic
anhydride;
1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene-2,3-dicarboxylic
anhydride; or 3,6-methano-1-methyl-1,2,3,6-tetrahydro-cis-phthalic
acid anhydride.
13. The process of claim 1, wherein said monomer is a norbornene
derivative containing at least one imide group.
14. The process of claim 13, wherein said norbornene derivative is
N-methyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide;
N-ethyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide;
N-propyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide;
N-n-butyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide;
N-octyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide,
N-cyclohexyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide;
N-phenyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide or
N-octyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene-2,3-dicar
boxyimide.
15. The process of claim 1, wherein said monomer is
1,4-dihydro-1,4-methanonaphthalene.
16. The process of claim 1, wherein said monomer is cyclopentene,
1,5-cyclooctadiene or bicyclo[2,2,1]-heptene-2.
17. The process of claim 1, wherein said organometallic compound is
represented by the formula
wherein M represents the metal belonging to group IA, IIA, IIB,
IIIB, IVA, or IVB of the periodic table; R represents an organic
group having at most 20 carbon atoms selected from an alkyl group,
an alkenyl group, an aryl group, an aralkyl group, an alkoxide
group, a phenoxy group, and a cyclopentadienyl group, a hydrogen
atom, or a halogen atom, the groups represented by R.sub.n may be
the same or different and at least one of said groups is the
organic group; n represents the maximum atomic valence number of
said metal or a positive integer of less than the maximum atomic
valence number.
18. The process of claim 17, wherein M represents aluminum.
19. The process of claim 18, wherein said organometallic compound
is triethylaluminum or diethylaluminum chloride.
20. The process of claim 1, wherein said organometallic compound is
aluminum siloxane represented by the formula ##STR25## wherein
R.sup.27, R.sup.28 and R.sup.29, which may be the same or
different, each represents a halogen atom, an alkyl group having at
most 10 carbon atoms, or an alkoxy groups having at most 10 carbon
atoms; R.sup.30 represents an alkyl group having at most 10 carbon
atoms; and R.sup.31 represents an alkyl group having at most 10
carbon atoms, an alkoxy group having at most 10 carbon atoms, or a
substituent having the formula ##STR26## where R.sup.32, R.sup.33
and R.sup.34, which may be the same or different, each has the same
meaning as R.sup.27, R.sup.28 and R.sup.29 above and n is a
positive integer less than 10.
21. The process of claim 20, wherein said aluminum siloxalane is
diethyl aluminum triethylsiloxalane.
22. The process of claim 1, wherein said organometallic compound is
a dialumoxane compound represented by the formula ##STR27## wherein
R.sup.39, R.sup.40 and R.sup.41, which may be the same or
different, each represents a halogen atom, an alkyl group having at
most 10 carbon atoms, or an alkoxy group having at most 10 carbon
atoms and R.sup.42 represents an alkyl group having at most 10
carbon atoms.
23. The process of claim 22, wherein said dialumoxane compound is
tetraethyl dialumoxane.
24. The process of claim 1, wherein said oxide is tungsten trioxide
or molybdenum trioxide.
25. The process of claim 1, wherein said phosphorus compound is
phosphorus pentachloride, phosphorus pentabromide, phosphorus
pentafluoride, or phosphorus oxytrichloride.
26. The process of claim 1, wherein said reaction product is
prepared at a temperature of 0.degree. to 250.degree. C in an inert
organic solvent.
27. The process of claim 1, wherein said ring-opening
polymerization is carried out in the presence of an unsaturated
polymer having carbon-carbon double bonds.
28. The process of claim 1, wherein said ring-opening
polymerization is carried out in the presence of a molecular weight
controlling agent.
29. The process of claim 1, wherein said catalyst system is
prepared from the organometallic compound, the reaction product,
and further a third component selected from the group consisting of
water, oxygen, an oxygen-containing organic compound, a
nitrogen-containing organic compound, a halogen-containing organic
compound, a phosphorus-containing compound, a sulfur-containing
compound, a metal-containing organic compound, a metal hydroxide, a
metal oxide, a metal halide, a metal chelate compound, a metal salt
and a reactive group-containing polymer.
30. The process of claim 29, wherein said phosphorus-containing
compound is a phosphate compound.
31. The process of claim 30, wherein said phosphate compound is a
halogen-containing phosphate compound represented by the
formula
wherein R.sup.43, R.sup.44 and R.sup.45, which may be the same or
different, each represents a hydrocarbon group having at most 20
carbon atoms or halogen-substituted hydrocarbon groups having at
most 20 carbon atoms, at least one of said R.sup.43, R.sup.44 and
R.sup.45 being a hydrocarbon group substituted with at least one
halogen atom.
32. The process of claim 31, wherein said a halogen-containing
phosphate compound is selected from the group consisting of
tris(.beta.-Chloro-ethyl) phosphate, tris(.beta.-bromo-ethyl)
phosphate, tris(2,3-dichloro-n-propyl) phosphate,
tris(2,3-dibromo-n-propyl) phosphate,
tris(2-bromo-3-chloro-n-propyl) phosphate, tris(3-chloro-n-propyl)
phosphate, tris(dichloroisopropyl) phosphate and
tris(2,4-dichloro-phenyl) phosphate.
33. The process of claim 5 wherein said norbornene derivative is
one of the compounds represented by general formulae (II), (III),
(IV) and (V): ##STR28## wherein W.sup.2, X.sup.2, Y.sup.2 and
Z.sup.2 in general formula (II) and W.sup.3, X.sup.3, Y.sup.3 and
Z.sup.3 in general formula (III) and W.sup.5, X.sup.5, Y.sup.5 and
Z.sup.5 in general formula (V), which may be the same or different,
each represents a hydrogen atom, an ester group represented by the
general formulae --COOR.sup.1 or --OCOR.sup.1 wherein R.sup.1
represents a hydrocarbon group having at most 20 carbon atoms, an
ester group-substituted hydrocarbon residue represented by the
general formulae --R.sup.2 COOR.sup.3 or --R.sup.2 OCOR.sup.3
wherein R.sup.3 has the same meaning as R.sup.1 and R.sup.2
represents a divalent hydrocarbon group having at most 20 carbon
atoms, or a hydrocarbon group having at most 20 carbon atoms, at
least one of said W.sup.2, X.sup.2, Y.sup.2 and Z.sup.2 and
W.sup.3, X.sup.3, Y.sup.3 and Z.sup.3 and W.sup.5 , X.sup.5,
Y.sup.5 and Z.sup.5 being said ester group or said ester
group-substituted hydrocarbon residue; wherein A represents
--COO--R.sup.4 -OOC-- or --COOR.sup.5 wherein R.sup.4 and R.sup.5
each represents an alkylene group having at most 20 carbon atoms;
and wherein W.sup.4 and Z.sup.4 in formula (IV), which may be the
same or different, each represents a hydrogen atom or a hydrocarbon
group having at most 20 carbon atoms.
34. The process of claim 7 wherein said norbornene derivative is
one of the compounds represented by the general formulae (VI),
(VII) and (VIII): ##STR29## wherein W.sup.6, X.sup.6, Y.sup.6 and
Z.sup.6 in general formula (VI) and W.sup.7, X.sup.7, Y.sup.7 and
Z.sup.7 in general formula (VII), which may be the same or
different, each represents a hydrogen atom, an ether group, a
hydrocarbon group having at most 20 carbon atoms or an ether
group-substituted hydrocarbon residue of the formula --R.sup.7
OR.sup.6 wherein R.sup.6 represents a hydrocarbon group having at
most 20 carbon atoms and R.sup.7 represents a divalent hydrocarbon
group having at most 20 carbon atoms, at least one of said W.sup.6,
X.sup.6, Y.sup.6 and Z.sup.6 and W.sup.7, X.sup.7, Y.sup.7 and
Z.sup.7 being said ether group or said ether group-substituted
hydrocarbon residue; wherein B represents --R.sup.8 OR.sup.9 or
--R.sup.10 O-- wherein R.sup.8, R.sup.9 and R.sup.10, which may be
the same or different, each represents a hydrocarbon group having
at most 20 carbon atoms; and wherein W.sup.8 and Z.sup.8 in general
formula (VIII), which may be the same or different, each represents
a hydrogen atom or a hydrocarbon group having at most 20 carbon
atoms.
35. The process of claim 9 wherein said norbornene derivative is
one of the compounds represented by general formulae (XI) and
(XII): ##STR30## wherein W.sup.11, X.sup.11, Y.sup.11 and Z.sup.11
in general formula (XI) and W.sup.12, X.sup.12, Y.sup.12 and
Z.sup.12 in general formula (XII), which may be the same or
different, each represents a hydrogen atom, a chlorine atom, a
bromine atom, a hydrocarbon group having at most 20 carbon atoms or
a hydrocarbon residue having at most 20 carbon atoms and
substituted by at least one chlorine or bromine atom, at least one
of said W.sup.11, X.sup.11, Y.sup.11 and Z.sup.11 and W.sup.12,
X.sup.12, Y.sup.12 and Z.sup.12 being a chlorine or bromine atom or
said hydrocarbon residue.
36. The process of claim 11 wherein said norbornene derivative is
one of the compounds represented by the general formulae (XIII) or
(XIV): ##STR31## wherein W.sup.13 and Z.sup.13 in general formula
(XIII) and W.sup.14 and X.sup.14 in general formula (XIV), which
may be the same or different, each represents a hydrogen atom or a
hydrocarbon group having at most 20 carbon atoms; wherein E
represents a tetravalent hydrocarbon group having from 4 to 20
carbon atoms; wherein F represents an oxygen atom; wherein l and m
each independently represents 1 or 2; and wherein q represents 0 or
1, wherein when q is 0, the carbon atoms of the norbornene ring
form a ring together with the acid anhydride-containing group.
37. The process of claim 13 wherein said norbornene derivative is
one of the compounds represented by the general formulae (XV) and
(XVI): ##STR32## wherein W.sup.15 and Z.sup.15 in general formula
(XV) and W.sup.16 and X.sup.16 in general formula (XVI), which may
be the same or different, each represents a hydrogen atom or a
hydrocarbon group having at most 20 carbon atoms; wherein E
represents a tetravalent hydrocarbon group having from 4 to 20
carbon atoms; wherein G represents a group of the formula
>N-R.sup.21 wherein R.sup.21 represents a hydrocarbon group
having at most 20 carbon atoms or a hydrocarbon residue having an
ester group; wherein l and m each independently represents 1 to 2;
and wherein q represents 0 or 1, wherein when q is 0, the carbon
atoms of the norbornene ring form a ring together with the imide
group-containing group.
Description
BACKGROUND OF THE INVENTION
The present invention relates to a process of producing
ring-opening polymerization products and more particularly it
relates to a process of producing a ring-opening polymerization
product at a high polymerization activity by subjecting a
norbornene derivative containing at least one polar group or
aromatic group, a norbornadiene derivative containing at least one
of said groups or a cycloolefin to a ring-opening polymerization in
the presence of, if desired, an unsaturated polymer, using a
catalyst system prepared from an organometallic compound and the
reaction product of tungsten oxide or molybdenum oxide and a
phosphorus pentahalide or phosphorus oxytrihalide or these
compounds and other third components. It has been discovered that a
novel and useful ring-opening polymerization product is obtained by
polymerizing a norbornene derivative containing at least one cyano
group, ester group, acid anhydride group, ether group, imide group,
halogen atom or aromatic group, norbornadiene derivatives
containing at least one of said groups, a cycloolefin or a mixture
of at least one of the aforesaid derivatives using a catalyst
system prepared from a tungsten compound or a molybdenum compound
and an organometallic compound or these compounds and other third
components such as, an organic peroxide, an acetalic compound, and
an alcoholic compound as described in the specifications of our
U.S. Pat. No. 3,856,758; Japanese Patent Application Laid Open Nos.
77,999/74; 58,200/75; 61,500/75; 71,800/75; 75,300/75; 103,600/75;
110,000/75 and 153,100/75.
Some of the ring-opening polymerization products obtained by the
aforesaid processes are superior to polyvinyl chloride resin and
polypropylene resin which have now been manufactured on an
industrial scale and widely used in various industrial fields in
not only the mechanical properties such as impact strength,
low-temperature impact strength and tensile strength but also heat
resistance and transparency. Furthermore, these polymerization
products can be fabricated or molded into various forms by applying
to a fabrication or molding method which has widely been employed
in the field of thermoplastic resins, such as injection molding,
extrusion molding, blow molding, compression molding and can be
used for various purposes as containers, films, sheets, pipers and
the like. Moreover, the properties of these polymerization products
can be improved for fitting desired purposes by blending together
with a thermoplastic resin such as a polyvinyl chloride riesin, a
polymethyl-methacrylate resin, etc.; said thermoplastic resin also
including an impact resistant resin such as an ABS resin and an ACS
resin; a heat resistant resin such as a polyacetal resin, a
polyamide resin, etc.; and/or a rubber-like material such as a
polybutadiene rubber, a chlorinated polyethylene rubber, etc., or
further by adding thereto various additives.
Still further, some other ring-opening polymerization products
prepared by the aforesaid processes can be used, as is or following
the polymer reaction, as ion-exchange resins, adhesives, and
flocculants.
Also, it has been proposed to produce a ring-opening polymerization
product by polymerizing a cycloolefinic compound such as
cyclopentene using a catalyst system comprising tungsten oxide
and/or molybdenum oxide and a Lewis acid such as aluminum chloride,
titanium tetrachloride, tin tetrachloride, vanadium tetrachloride,
etc., or these components and an organometallic compound of a metal
belonging to Groups I to IV of the periodic table, in particular an
organoaluminum compound as described in the specifications of
Japanese Patent Application Laid Open Nos. 17,389/72; 39,388/72;
and 39,599/73. The polymerization products obtained by these
processes are suitable as rubber-like materials owing to their
excellent elastic property.
Furthermore, it has been discovered that the same ring-opening
polymerization products of the norbornene derivatives as mentioned
above can be obtained by using the catalyst system described in the
above-mentioned specifications (Japanese Patent Application No.
18470/74). However, even if a cycloolefin or norbornene derivative
is polymerized in the presence of a catalyst system comprising
tungsten trioxide and aluminum chloride or these compounds and an
organoaluminum compound which is described as having the highest
polymerization activity in the above-mentioned specifications, the
polymerization activity is yet unsatisfactory.
Since the polar group present in the monomer as used in the present
invention is known to inactivate the catalyst system thereby
markedly decreasing the catalytic activity, attempts to obtain
catalyst systems possessing excellent catalytic activity for the
ring-opening polymerization of norbornene derivatives containing a
polar group have not succeeded.
SUMMARY OF THE INVENTION
It is, therefore, a primary objective of the present invention to
provide a process of producing ring-opening polymerization products
of a norbornene derivative containing at least one polar group or
aromatic group, a norbornadiene derivative containing at least one
of said groups or a cycloolefin using a catalyst system possessing
excellent catalytic activity.
Other objects, features and advantages will be apparent from the
following detailed discussion.
The above and other objects are achieved in a process of producing
a ring-opening polymerization product which comprises ring-opening
polymerizing the norbornene derivative, norbornadiene derivative or
cycloolefin in the presence of, if desired, an unsaturated polymer
having a carbon-carbon double bond (the polymer is referred to
hereafter as "unsaturated polymer") using the catalyst system
prepared from an organometallic compound and the reaction product
of at least one of tungsten oxide and molybdenum oxide and at least
one of phosphorus pentahalide and phosphorus oxytrihalide, or these
compounds and other third components.
That is, according to the present invention, there is provided a
process of producing a ring-opening polymerization product which
comprises ring-opening polymerizing in the presence or absence of
an unsaturated polymer having a carbon-carbon double bond at least
one of the norbornene derivatives each containing at least a polar
group selected from the group consisting of a nitrile group, an
ester group, an ether group, an amide group, a halogen atom, an
acid anhydride group, an imide group and an aromatic
nitrogen-containing heterocyclic group or an aromatic group, a
norbornadiene derivative containing at least one said groups or a
cycloolefin using the catalyst system prepared from (A) an
organometallic compound of a metal belonging to Groups IA, IIA,
IIB, IIIB, IVA, or IVB of the periodic table and (B) the reaction
product of at least one of tungsten oxide and molybdenum oxide and
at least one of phosphorus pentahalide and phosphorus
oxytrihalide.
Since the catalyst system used in this invention possesses quite a
high polymerization activity (or catalytic activity) and hence can
give a high production yield of the ring-opening polymerization
product per unit amount of catalyst or in other words, a small
amount of the catalyst is sufficient for producing a definite
amount of the ring-opening polymerization product, not only the
amount of catalyst used can be reduced but also the production
efficiency of the polymerization apparatus can be increased in the
case of using the catalyst. In this case, furthermore, the amount
of the catalyst present in the polymerization system is less since
the amount of it required for the polymerization reaction may be
less and thus after the polymerization is finished, the catalyst
residue remaining in the ring-opening polymerization product thus
obtained can be easily removed therefrom for preventing the
occurrence of coloring and deterioration of the ring-opening
polymerization product owing to the less amount of the catalyst
residue in the product. Moreover, since the catalyst system of this
invention shows less reduction in catalytic activity in the
ring-opening polymerization or has a long catalytic life, the
ring-opening polymerization can be carried out continuously for a
long period of time.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Preferred norbornene derivatives containing at least one polar
group or aromatic group include a norbornene derivative containing
at least one nitrile group, a norbornene derivative containing at
least one ester group, a norbornene derivative containing at least
one ether group, a norbornene derivative containing at least one
amide group, a norbornene derivative containing at least one
halogen atom, a norbornene derivative containing at least one acid
anhydride group, a norbornene derivative containing at least one
imide group, a norbornene derivative containing at least one
aromatic nitrogen-containing heterocyclic group, a norbornene
derivative containing at least one aromatic group, a mixture of the
aforesaid norbornene derivatives and a mixture of more than 50 mole
percent of the aforesaid norbornene derivative and an unsaturated
cyclic compound.
The norbornene derivative containing at least one nitrile group
(referring at "cyano type norbornene derivative") contains at least
one nitrile group or a hydrocarbon residue substituted by said
nitrile group at the 5 and/or 6 positions of
bicyclo[2,2,1]-heptene-2 as shown in the following general formula
(I): ##STR1## wherein W.sup.1, X.sup.1, Y.sup.1 and Z.sup.1, which
may be the same or different, each represents a hydrogen atom, a
nitrile group, or a hydrocarbon group selected from the group
consisting of an alkyl group having at most 20 carbon atoms, a
cycloalkyl group having at most 20 carbon atoms, an alkenyl group
having at most 20 carbon atoms and an aryl group having at most 20
carbon atoms, said hydrocarbon group having or not having a nitrile
group, at least one of W.sup.1, X.sup.1, Y.sup.1 and Z.sup.1 being,
however, a nitrile group or the hydrocarbon residue substituted
with a nitrile group.
Examples of the hydrocarbon groups represented by W.sup.1, X.sup.1,
Y.sup.1 and Z.sup.1 of general formula (I) are methyl, ethyl,
n-propyl, isobutyl, n-butyl, hexyl, octyl, dodecyl, tetradecyl,
hexadecyl, eicosyl, phenyl, naphthyl, tolyl, cyclohexyl,
1-methylcyclohexyl and 2-octenyl.
Typical cyano type norbornene derivatives are
5-cyano-bicylo-[2,2,1]-heptene-2;
5,5-dicyano-bicylo[2,2,1]-heptene-2;
5,6-dicyano-bicyclo[2,2,1]-heptene-2;
5-cyano-5-methyl-bicyclo[2,2,1]-heptene-2;
5-cyano-6-methyl-bicyclo[2,2,1]-heptene-2;
5-cyano-5-ethyl-bicyclo[2,2,1]-heptene-2;
5-cyano-5-octyl-bicyclo[2,2,1]-heptene-2;
5-cyano-6-phenyl-bicyclo[2,2,1]-heptene-2; 5-cyano-5,
6-dimethyl-bicyclo[2,2,1]-heptene-2;
5-cyanomethyl-bicyclo[2,2,1]-heptene-2;
5-.omega.-cyanoheptyl-bicyclo[2,2,1]-heptene-2;
5-cyano-6-cyclohexyl-bicyclo-[2,2,1]-heptene-2,
5-.omega.-cyano-2-decenyl-bicyclo[2,2,1]-heptene-2,
5-cyano-bicyclo[2,2,1]-heptene-2;
5,5-dicyano-bicyclo[2,2,1]-heptene-2;
5,6-dicyano-bicyclo[2,2,1]-heptene-2;
5-cyano-5-methyl-bicyclo[2,2,1]-heptene-2;
5-cyano-5-methyl-bicyclo[2,2,1]-heptene-2 and
5-cyanomethyl-bicyclo[2,2,1]-heptene-2.
Furthermore, other examples of the cyano type norbornene
derivatives used in this invention are described in the
specification of, for example, U.S. Pat. No. 3,856,758.
The norbornene derivatives containing at least one ester group
(referred to as "ester type norbornene derivative") are represented
by general formula (II) and general formula (III) ##STR2## wherein
W.sup.2, X.sup.2, Y.sup.2 and Z.sup.2 in general formula (II) and
W.sup.3, X.sup.3, Y.sup.3 and Z.sup.3 in general formula (III),
each represents a hydrogen atom, an ester group represented by the
general formula --COOR.sup.1 or --OCOR.sup.1 (wherein R.sup.1
represents a hydrocarbon group having at most 20 carbon atoms), a
hydrocarbon residue substituted with an ester group, represented by
the general formula --R.sup.2 COOR.sup.3 or --R.sup.2 OCOR.sup.3
(wherein R.sup.3 represents a hydrocarbon group having at most 20
carbon atoms and R.sup.2 represents a divalent hydrocarbon group
having at most 20 carbon atoms), or a hydrocarbon group having at
most 20 carbon atoms, at least one of said W.sup.2, X.sup.2,
Y.sup.2 and Z.sup.2 or W.sup.3, X.sup.3, Y.sup.3 and Z.sup.3 being,
however, the ester group or the hydrocarbon residue substituted
with an ester group.
Also, other ester type norbornene derivatives are represented by
general formula (IV) and general formula (V) ##STR3## wherein A
represents --COO--R.sup.4 --OOC-- or --COOR.sup.5 -- (where R.sup.4
and R.sup.5 each represents an alkylene group having at most 20
carbon atoms); W.sup.4 and Z.sup.4, being identical or different,
each represents a hydrogen atom or a hydrocarbon group having at
most 20 carbon atoms, and W.sup.5, X.sup.5, Y.sup.5 and Z.sup.5,
which may be the same or different, each represents a hydrogen atom
or the ester group the hydrocarbon group having at most 20 carbon
atoms or the hydrocarbon residue substituted with an ester group as
described above in connection with formulas (II) and (III), at
least one of said W.sup.5, X.sup.5, Y.sup.5 and Z.sup.5 being,
however, the ester group of the hydrocarbon residue substituted
with the ester group.
In the practice of the process of this invention, the ester type
norbornene derivatives represented by general formula (II) are most
desirable among the ester type norbornene derivatives shown by
above-indicated general formulae (II) to (V).
Practical examples of the desirable ester type norbornene
derivatives of general formula (II) are
5-methoxycarbonyl-bicyclo[2,2,1]-heptene-2;
5-ethoxycarbonyl-bicyclo[2,2,1]-heptene-2;
5-butoxycarbonyl-bicyclo[2,2,1]-heptene-2;
5-allyloxycarbonyl-bicyclo[2,2,1]-heptene-2;
5-methyl-5-methoxycarbonyl-bicyclo[2,2,1]-heptene-2;
5-hexyloxycarbonyl-6-methyl-bicyclo[2,2,1]-heptene-2;
5-ethoxycarbonyl-6-phenyl-bicyclo[2,2,1]-heptene-2;
5-heptyl-6-octyloxycarbonyl-bicyclo[2,2,1]-heptene-2;
5-methoxycarbonyl-6-methoxycarbonylmethyl-bicyclo[2,2,1]-heptene-2;
5,6-dimethoxycarbonyl-bicyclo[2,2,1]-heptene-2;
5,6-diethoxycarbonyl-bicyclo[2,2,1]-heptene-2;
5,5-dibutoxycarbonyl-bicyclo[2,2,1]-heptene-2;
5-methyl-6,6-dimethoxycarbonyl-bicyclo[2,2,1]-heptene-2;
5-.omega.-methoxycarbonylheptyl-6-octyl-bicyclo[2,2,1]-heptene-2;
5-.omega.-methoxycarbonyl-2-decenyl-6-pentyl-bicyclo[2,2,1]-heptene-2;
5-.omega.-methoxycarbonylheptyl-6-2-octenyl-bicyclo[2,2,1]-heptene-2;
5-acetoxymethyl-bicyclo[2,2,1]-heptene-2;
5-propoxymethyl-bicyclo[2,2,1]-heptene-2; and
5-stearoxymethyl-bicyclo[2,2,1]-heptene-2, with
5-methoxycarbonyl-bicyclo[2,2,1]-heptene-2;
5-ethoxycarbonyl-bicyclo-[2,2,1]-heptene-2;
5-butoxycarbonyl-bicyclo[2,2,1]-heptene-2;
5-allyloxycarbonyl-bicyclo[2,2,1]-heptene-2;
5-methyl-5-methoxycarbonyl-bicyclo[2,2,1]-heptene-2;
5-methoxycarbonyl-6-methoxycarbonylmethyl-bicyclo[2,2,1]-heptene-2;
5,6-dimethoxycarbonyl-bicyclo[2,2,1]-heptene-2;
5,6-diethoxycarbonyl-bicyclo[2,2,1]-heptene-2;
5,5-dibutoxycarbonyl-bicyclo[2,2,1]-heptene-2;
5-acetoxymethyl-bicyclo[2,2,1] -heptene-2;
5-propoxymethyl-bicyclo[2,2,1]-heptene-2 and
5-stearoxymethyl-bicyclo-[2,2,1]-heptene-2.
Similarly, practical examples will be easily found of the ester
type norbornene derivatives shown by general formulae (III), (IV)
and (V).
The norbornene derivatives containing at least one ether group
(referred to as "ether type norbornene derivative") are represented
by general formulae (VI), (VII) and (VIII) ##STR4## wherein
W.sup.6, X.sup.6, Y.sup.6 and Z.sup.6 in general formula (VI) and
W.sup.7, X.sup.7, Y.sup.7 and Z.sup.7 in general formula (VII),
which may be the same or different, each represents a hydrogen
atom, an ether group, or a hydrocarbon residue substituted with the
ether group, represented by the general formula --R.sup.7 OR.sup.6
(where R.sup.6 represents a hydrocarbon group having at most 20
carbon atoms and R.sup.7 represents a divalent hydrocarbon group
having at most 20 carbon atoms) or a hydrocarbon group having at
most 20 carbon atoms, at least one of said W.sup.6, X.sup.6,
Y.sup.6 and Z.sup.6 or W.sup.7, X.sup.7, Y.sup.7 and Z.sup.7 being,
however, an ether group or the hydrocarbon residue substituted with
an ether group; and W.sup.8 and Z.sup.8 in general formula (VIII),
which may be the same or different, each represents a hydrogen atom
or a hydrocarbon group having at most 20 carbon atoms, and B
represents --R.sup.8 OR.sup.9 -- or --R.sup.10 O-- (where R.sup.8,
R.sup.9, and R.sup.10 which may be the same or different, each
represents a hydrocarbon group having at most 20 carbon atoms).
Practical examples of the ether type norbornene derivatives shown
by general formula (VI) are 5-methoxy-bicyclo[2,2,1]-heptene-2;
5-n-propoxy-bicyclo-[2,2,1]-heptene-2;
5-isopropoxy-bicyclo[2,2,1]-heptene-2;
5-n-butoxy-bicyclo[2,2,1]-heptene-2;
5-octoxy-bicyclo-[2,2,1]-heptene-2;
5-cyclohexoxy-bicyclo[2,2,1]-heptene-2;
5-methoxymethyl-bicyclo[2,2,1]-heptene-];
5-isobutoxymethyl-bicyclo[2,2,1]-heptene-2;
5-methoxy-6-methoxymethyl-bicyclo[2,2,1]-heptene-2 and
5-phenoxy-bicyclo[2,2,1]-heptene-2.
Similarly, practical examples will also be found about the ether
type norbornene derivatives represented by general formulae (VII)
and (VIII).
Also, the norbornene derivatives containing at least one amide
group (referred to as "amide type norbornene derivative") are
represented by general formulae (IX) and (X) indicated above
##STR5## wherein W.sup.9, X.sup.9, Y.sup.9 and Z.sup.9 in general
formula (IX), which may be the same or different, each represents a
hydrogen atom, an amide group represented by the general formula
##STR6## (where R.sup.11 and R.sup.12, which may be the same or
different, each represents a hydrocarbon group having at most 20
carbon atoms), an amide group containing hydrocarbon residue
represented by the formula ##STR7## (where R.sup.13 and R.sup.14,
which may be the same or different, each represents a hydrocarbon
group having at most 20 carbon atoms and R.sup.15 represents a
hydrocarbon group having at most 20 carbon atoms), or the
hydrocarbon group having at most 20 carbon atoms; at least one of
said W.sup.9, X.sup.9, Y.sup.9 and Z.sup.9 being the amide group or
the amide group-containing hydrocarbon residue; D in general
formula (X) represents ##STR8## (where R.sup.16, R.sup.17, and
R.sup.18, which may be the same or different, each represents a
hydrocarbon group having at most 20 carbon atoms and R.sup.19
represents an alkylene group having at most 20 carbon atoms); and
W.sup.10 and Z.sup.10 in general formula (X), which may be the same
or different, each represents a hydrogen atom or a hydrocarbon
group having at most 20 carbon atoms.
Furthermore, in the present invention, the amide type norbornene
derivatives of the general formula (IX) indicated above wherein at
least one of W.sup.9, X.sup.9, Y.sup.9 and Z.sup.9 is a group
represented by the general formula ##STR9## (where R.sup.20
represents an alkylene group having at most 20 carbon atoms) may be
used as the monomers.
Practical examples of the amide type norbornene derivatives are
N,N-dimethyl-bicyclo[2,2,1]-heptene-2-carbonamide-5;
N,N-dibutyl-bicyclo[2,2,1]-heptene-2-carbonamide-5;
N-methyl-N-octyl-bicyclo[2,2,1]-heptene-2-carbonamide-5;
N-methyl-N-cyclohexyl-bicyclo[2,2,1]-heptene-2-carbonamide-5;
N-methyl-N-phenyl-bicyclo[2,2,1]-heptene-2-carbonamide-5;
N,N-dicyclohexyl-bicyclo[2,2,1]-heptene-2-carbonamide-5;
N,N-dibenzyl-bicyclo[2,2,1]-heptene-2-carbonamide-5;
N,N,-dimethyl-5-methyl-bicyclo[2,2,1]heptene-2-carbonamide-5;
N,N,-diethyl-6-methyl-bicyclo[2,2,1]-heptene-2-carbonamide-5;
N,N-dimethyl-6-phenyl-bicyclo[2,2,1]-heptene-2-carbonamide-5;
N,N,N',N'-tetramethyl-bicyclo-[2,2,1]-heptene-2-dicarbonamide-5,6
and
N,N,N',N'-tetraethylbicyclo-[2,2,1]-heptene-2-dicarbonamide-5,6.
The norbornene derivatives containing at least one halogen atom
(referred to as "halogen type norbornene derivative") are
represented by general formulae (XI) and (XII), ##STR10## wherin
W.sup.11, X.sup.11, Y.sup.11 and Z.sup.11 in general formula (XI)
and W.sup.12, X.sup.12, Y.sup.12 and Z.sup.12 in general formula
(XII), which may be the same or different, each represents a
hydrogen atom, a chlorine atom, a bromine atom, a hydrocarbon
residue having at most 20 carbon atoms and having at least one
chlorine atom or bromine atom, or a hydrocarbon group having at
most 20 carbon atoms, at least one of said W.sup.11, X.sup.11,
Y.sup.11 and Z.sup.11 or W.sup.12, X.sup.12, Y.sup.12 and Z.sup.12
being a chlorine atom, a bromine atom, or the hydrocarbon residue
having a chlorine atom or a bromine atom.
Practical examples of the halogen type norbornene derivatives are
5-chloro-bicyclo[2,2,1]-heptene-2;
5-chloro-5-methyl-bicyclo[2,2,1]-heptene-2;
5-chloro-6-methyl-bicyclo[2,2,1]-heptene-2;
5-chloromethyl-bicyclo[2,2,1]-heptene-2;
5,5-dichloro-bicyclo[2,2,1]-heptene-2;
5,6-dichloro-bicyclo[2,2,1]-heptene-2;
5,5-bis-(chloromethyl)-bicyclo[2,2,1]-heptene-2;
5,6-bis-(chloromethyl)-bicyclo[2,2,1]-heptene-2;
5,5-dichloro-6-methyl-bicyclo[2,2,1]-heptene-2;
--5-chloro-6-chloromethyl-bicyclo[2,2,1]-heptene-2;
5,6-dichloro-5-methyl-bicyclo[2,2,1]-heptene-2;
5-(.alpha.,.beta.-dichloroethyl)-bicyclo[2,2.k]-heptene-2;
5-chloro-5-methyl-6-chloromethyl-bicyclo[2,2,1]-heptene-2;
5-chloromethyl-5-methyl-6-chloro-bicyclo[2,2,1]-heptene-2;
5,5,6-trichloro-bicyclo[2,2,1]-heptene-2;
5,5,6,6-tetrachloro-bicyclo[2,2,1]-heptene-2, and
5-bromomethyl-bicyclo[2,2,1]-heptene-2, with
5-chloro-bicyclo[2,2,1]-heptene-2;
5-chl-ro-5-methyl-bicyclo-[2,2,1]-heptene-2;
5-chloro-6-methyl-bicyclo[2,2,1]-heptene-2;
5-chloromethyl-bicyclo[2,2,1]-heptene-2,
5,5,-dichloro-bicyclo-[2,2,1]-heptene-2;
5,6-dichloro-bicyclo[2,2,1]-heptene-2;
5,5-bis(chloromethyl)-bicyclo[2,2,1]-heptene-2 and
5,6-bis-(chloromethyl)-bicyclo[2,2,1]-heptene-2.
Furthermore, the halogen type norbornene derivatives illustrated
above as the practical examples in which at least one chlorine atom
is replaced by a bromine atom can be also shown as other typical
examples of them. Still other examples of the halogen type
norbornene derivatives used as the monomers in this invention are
described in the specification of Japanese Patent Application Nos.
125, 981/74.
The norbornene derivatives containing at least one acid anhydride
group (referred to as "acid anhydride norbornene derivatives") are
shown by general formulae (XIII) and (XIV) ##STR11## wherein
W.sup.13 and Z.sup.13 or W.sup.14 and X.sup.14, which may be the
same or different, each represents a hydrogen atom or a hydrocarbon
group having at most 20 carbon atoms; E represents a tetravalent
hydrocarbon group having 4 to 20 carbon atoms; F represents an
oxygen atom; l and m each represents independently 1 or 2; and q
represents 0 or 1.
When q is 0 in the aforesaid general formulae (XIII) and (XIV), the
carbon atoms of the norbornene ring form a single ring together
with the acid anhydride-containing group.
Practical examples of the acid anhydride type norbornene
derivatives are 3,6-methylene-1,2,3,6-tetrahydro-cis-phthalic
anhydride; 5-(5-carboxy-bicyclo[2,2,1]-hepta-2-enyl)acetic
anhydride;
2-oxo-1,3-dioxo-5,8-methano-1,2,3,4,4a,5,8,8a-octahydronaphthalene;
5,8-methano-1,2,3,4,4a,5,8,8a-octahydronaphthalene-2,3-dicarboxylic
anhydride;
1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene-2,3-dicarboxylic
anhydride;
2-oxa-1,3-dioxo-5,8,9,10-dimethano-1,2,3,4,4a,5,8,8a,9,9a,10,10a-dodecahyd
roanthracene; 3,6-methano-1-methyl-1,2,3,6-tetrahydro-cis-phthalic
acid anhydride; 3,6-methano-1-butyl-1,2,3,6-tetrahydro-cis-phthalic
anhydride; and 3,6-methano-1-octyl-1,2,3,6-tetrahydro-cis-phthalic
anhydride, with 3,6-methylene-1,2,3,6-tetrahydro-cis-phthalic
anhydride;
5,8-methano-1,2,3,4,4a,5,8,8a-octahydronaphthalene-2,3-dicarboxylic
anhydride;
1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene-2,3-dicarboxylic
anhydride and 3,6-methano-1-methyl-1,2,3,6-tetrahydro-cis-phthalic
acid anhydride.
Other examples of the acid anhydride type norbornene derivatives
are described in the specification of Japanese Patent Application
Laid Open No. 58,200/75.
The norbornene derivatives containing at least one imide group
(referred as "imide type norbornene derivatives") are shown by
general formulae (XV) and (XVI) ##STR12## wherein, G represents a
group having a general formula >N -- R.sup.21 (where R.sup.21
represents a hydrocarbon group having at most 20 carbon atoms or a
hydrocarbon residue having an ester group) W.sup.15 and Z.sup.15
have the same meaning as W.sup.13 and Z.sup.13, W.sup.16 and
X.sup.16 have the same meaning as W.sup.14 and X.sup.14, and E, l,
m, and q have the same meaning as above.
Other examples of the imide type norbornene derivatives used in
this invention are shown by the following general formula (XVII)
##STR13## wherein W.sup.17, Y.sup.17 and Z.sup.17, which may be the
same or different, each represents a hydrogen atom or a hydrocarbon
group having at most 20 carbon atoms; R.sup.22 represents an
alkylene group having 2-6 carbon atoms, an alkenylene group, or an
arylene group; and n represents 0, 1, or 2.
Practical examples of the imide type norbornene derivatives are
N-methyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide;
N-ethyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide;
N-propyl-3,6-methylene-1,2,3,6-te-rahydro-cis-p-thalimide;
N-n-butyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide;
N-octyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide,
N-cyclohexyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide;
N-phenyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide;
N-methoxy-carbonylmethyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide;
N-ethoxycarbonyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide;
N-butoxycarbonyl-3,6-methylene-1,2,3,6-tetrahydro-cis-1-methyl-1,2,3,6-tet
rahydro-cis-phthalimide;
N-butyl-3,6-methylene-1-butyl-1,2,3,6-tetrahydro-cis-phthalimide;
bicyclo[2,2,1]-hepta-2-ene-5-spiro-3'-N-butyl succinimide;
2-butyl-2-aza-1,3-dioxo-5,8-methano-1,2,3,4,4a,5,8,8a-octahydronaphthalene
;
N-octyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene-2,3-dica
rboxyimide;
5-maleimidomethyl-bicyclo-[2,2,1]-heptene-2,5-citraconimidomethyl-bicyclo[
2,2,1]-heptene-2,5-glutaconimidomethyl-bicyclo[2,2,1]-heptene-2;
5-succinimidomethyl-bicyclo[2,2,12-heptene-2; and
5-phthalimidomethyl-bicyclo-[2,2,1]-heptene-2, with
N-methyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide;
N-ethyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide;
N-propyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide;
N-n-butyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide;
N-octyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide,
N-cyclohexyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide;
N-phenyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide; and
N-octyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene-2,3-dicar
boxyimide.
Furthermore, still other general formulae of the imide type
norbornene derivatives, the production process of them, typical
examples of the
N-substituted-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide
compounds of the imide type norbornene derivatives, the
N-(5-norborna-2-enyl) substituted maleimide compounds of them and
typical examples of other imide type norbornene derivatives are
described in the specification of Japanese Patent Application Laid
Open No. 75,300/75.
The norbornene derivatives containing at least one aromatic
nitrogen-containing heterocyclic group (referred to as "aromatic
nitrogen-containing heterocyclic type norbornene derivatives") are
the norbornene derivatives each containing a heterocyclic ring
having at least one nitrogen atom in said ring (see, the item
"Aromatic Character" of "Kagaku Dai Jiten (Chemical Encyclopedia)";
Vol. 8, page 601, 1969, published by Kyoritsu Publishing Co.).
The aromatic nitrogen-containing heterocyclic type norbornene
derivatives are shown by general formulae (XVIII) and (XIX)
indicated above, ##STR14## wherein, W.sup.18, X.sup.18, Y.sup.18
and Z.sup.18 in general formula (XVIII) or W.sup.19, X.sup.19,
Y.sup.19 and Z.sup.19 in general formula (XIX), which may be the
same or different, each represents a hydrogen atom; an alkyl group
having at most 10 carbon atoms; an aromatic nitrogen-containing
heterocyclic group selected from the group consisting of a pyridine
group, a quinoline group, and a carbazole group; or the aromatic
nitrogen-containing heterocyclic group substituted by an alkyl
group having at most 20 carbon atoms, at least one of said
W.sup.18, X.sup.18, Y.sup.18 and Z.sup.18 or W.sup.19, X.sup.19,
Y.sup.19 and Z.sup.19 being said aromatic nitrogen-containing
heterocyclic group or said alkyl-substituted aromatic
nitrogen-containing heterocyclic group.
Practical examples of the aromatic nitrogen-containing heterocyclic
type norbornene derivatives are
5-(2'-pyridyl)-bicyclo[2,2,1]-heptene-2;
5-(3'-pyridyl)-bicyclo[2,2,1]-heptene-2;
5-(4'-pyridyl)-bicyclo[2,2,1]-heptene-2;
5-(3'-methyl-2'-pyridyl)-bicyclo[2,2,1]-heptene-2;
5-(4'-methyl-2'-pyridyl)-bicyclo[2,2,1]-heptene-2;
5-(5'-methyl-2'-pyridyl)-bicyclo[2,2,1]--eptene-2;
5-(2'-ethyl-3'-pyridyl)-bicyclo[2,2,1]-heptene-2;
5-(3'-butyl-4'-pyridyl)-bicyclo[2,2,1]-heptene-2;
5-(2'-quinolyl)-bicyclo[2,2,1]-heptene-2;
5-(3'-quinolyl)-bicyclo[2,2,1]-heptene-2;
5-(4'-quinolyl)-bicyclo[2,2,1]-heptene-2;
5-(9'-carbazolyl)-bicyclo-[2,2,1]-heptene-2;
5-(3'-methyl-9-carbazolyl)-bicyclo[2,2,1]-heptene-2;
5-(3'-ethyl-9'-carbazolyl)-bicyclo[2,2,1]-heptene-2;
5-(3'-n-decyl-9'-carbazolyl)-bicyclo[2,2,1]-heptene-2;
5-(9'-methyl-3'-carbazolyl)-bicyclo[2,2,1]-heptene-2; 5-(
9'-n-butyl-3'-carbazolyl)-bicyclo[2,2,1]-heptene-2;
5-(9'-n-octyl-3'-carbazolyl)-bicyclo[2,2,1]-heptene-2; and
2-(2'-pyridyl)-1,4;
5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.
Other typical examples of the aromatic nitrogen-containing
heterocyclic type norbornene derivatives are described in the
specification of Japanese Patent Application No. 15,310/'74.
The norbornene derivatives containing at least one aromatic group
(referred as "aromatic type norbornene derivative") are represented
by general formulae (XX) and (XXI), ##STR15## wherein, W.sup.20,
X.sup.20, Y.sup.20 and Z.sup.20 or W.sup.21, X.sup.21, Y.sup.21 and
Z.sup.21, which may be the same or different, each represents a
hydrogen atom, an alkyl group having at most 20 carbon atoms, a
cycloalkyl group having at most 20 carbon atoms, an alkenyl group
having at most 20 carbon atoms or an aromatic hydrocarbon group
substituted by a hydrocarbon group having at most 30 carbon atoms,
said aromatic hydrocarbon group having at most 3 aromatic rings,
and at least one of said W.sup.20, X.sup.20, Y.sup.20 and Z.sup.20
or W.sup.21, X.sup.21, Y.sup.21 and Z.sup.21 being said aromatic
hydrocarbon group. Examples of the formulae of these aromatic
hydrocarbon groups are clearly shown in the specification of
Japanese Patent Application Nos. 61,851/74 together with the
typical examples of the hydrocarbon groups as the substituents for
the aromatic hydrocarbon groups.
Practical examples of the aromatic type norbornene derivatives are
5-phenyl-bicyclo[2,2,1]-heptene-2;
5-methyl-5-phenyl-bicyclo[2,2,1]-heptene-2;
5-ethyl-5-phenyl-bicyclo[2,2,1]-heptene-2;
5-n-butyl-6-phenyl-bicyclo[2,2,1]-heptene-2;
5-p-tolyl-bicyclo[2,2,1]-heptene-2;
5,6-diphenyl-bicyclo[2,2,1]-heptene-2;
5-.alpha.-naphthyl-bicyclo[2,2,1]-heptene-2;
5-anthryl-bicyclo[2,2,1]-heptene-2; 2-phenyl-1,4;
5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene;
2-methyl-2-phenyl-1,4;
5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene;
2-p-tolyl-1,4;
5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene; and
2,3-diphenyl-1,4;
5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.
Other typical examples of the aromatic type norbornene derivatives
are described in the specification of Japanese Patent Application
Nos. 61,851/'74.
Preferred norbornadiene derivatives containing at least one polar
group or aromatic group include a norbornadiene derivative
containing at least one of the polar groups described in the above
norbornene derivatives and a norbornadiene derivative containing at
least one aromatic group.
The norbornadiene derivative containing at least one ester group
(referred to as "ester type norbornadiene derivative") is the most
preferable norbornadiene derivative containing at least one polar
group.
The ester type norbornadiene derivatives are shown by following
general formula (XXII) ##STR16## wherein X.sup.22 and Y.sup.22,
which may be the same or different, each represents a hydrogen
atom; a hydrocarbon group having at most 20 carbon atoms; or the
ester-containing hydrocarbon residue represented by the general
formula --(CH.sub.2)mCOOR.sup.23 or --(CH.sub.2)nOCOR.sup.24 (where
R.sup.23 and R.sup.24 each represents a hydrocarbon group having at
most 20 carbon atoms and m and n each represents 0 or an integer of
1-10), at least one of said X.sup.22 and Y.sup.22 being the
ester-containing hydrocarbon residue.
Practical examples of the ester type norbornadiene derivatives are
2-methoxycarbonyl-bicyclo[2,2,1]-hepta-2,5-diene;
2-ethoxycarbonyl-bicyclo[2,2,1]-hepta-2,5-diene;
2-propyloxycarbonyl-bicyclo[2,2,1]-hepta-2,5-diene;
2-butyloxycarbonyl-bicyclo[2,2,1]-hepta-2,5-diene;
2-pentyloxycarbonyl-bicyclo[2,2,1]-hepta-2,5-diene;
2-hexyloxycarbonyl-bicyclo[2,2,1]-hepta-2,5-diene;
2-octyloxycarbonyl-bicyclo[2,2,1]-hepta-2,5-diene;
2-decyloxycarbonyl-bicyclo[2,2,1]-hepta-2,5-diene;
2-methoxycarbonyl-3-methyl-bicyclo[2,2,1]-hepta-2,5-diene;
2-methoxycarbonyl-3-ethylbicyclo[2,2,1]-hepta-2,5-diene;
2,3-dimethoxycarbonyl-bicyclo[2,2,1]-hepta-2,5-diene;
2,3-diethoxycarbonyl-bicyclo[2,2,1]-hepta-2,5-diene;
2,3-dipropyloxycarbonyl-bicyclo[2,2,1]-hepta-2,5-diene;
2,3-dibutyloxycarbonyl-bicyclo[2,2,1]-hepta-2,5-diene;
2,3-dipentyloxycarbonyl-bicyclo[2,2,1]-hepta-2,5-diene;
2,3-dihexyloxycarbonyl-bicyclo[2,2,1]-hepta-2,5-diene;
2-acetoxymethylbicyclo[2,2,1]-hepta-2,5-diene;
2-propionyloxymethyl-bicyclo[2,2,1]-hepta-2,5-diene;
2-butyryloxymethyl-bicyclo[2,2,1]-hepta-2,5-diene;
2-vareryloxymethyl-bicyclo[2,2,1]-hepta-2,5-diene;
2caprolyloxy-bicyclo[2,2,1]-hepta-2,5-diene;
2-capryloxymethyl-bicyclo[2,2,1]-hepta-2,5-diene;
2,3-di(acetoxymethyl)-bicyclo[2,2,1]-hepta-2,5-diene;
2,3-di(propionyloxymethyl)-bicyclo[2,2,1]-hepta-2,5-diene;
2,3-di(butyryloxymethyl)-bicyclo[2,2,1]-hepta-2,5-diene;
2-methoxycarbonylmethyl-bicyclo[2,2,1]-hepta-2,5-diene;
2-ethoxycarbonylmethyl-bicyclo [2,2,1]-hepta-2,5-diene; and
2-propyloxycarbonylmethyl-bicyclo[ 2,2,1]-hepta-2,5-diene.
The aromatic norbornadiene derivatives are the compounds in which
the carbon atoms occupying the 5- and 6-positions of
bicyclo[2,2,1]-heptene-2 concurrently constitute the two adjacent
carbon atoms of an aromatic cyclic compound. The aromatic type
norbornadiene derivatives are shown by the following general
formulae (XXIII) and (XXIV), ##STR17## wherein E.sup.1, E.sup.2,
E.sup.3, E.sup.4, E.sup.5 and E.sup.6, which may be the same or
different, each represents a hydrogen atom, a hydrocarbon group
selected from the group consisting of an alkyl group having at most
10 carbon atoms, an alkenyl group having at most 10 carbon atoms, a
cycloalkyl group having at least 10 carbon atoms, an aryl group
having at most 10 carbon atoms, and an aralkyl group having at most
10 carbon atoms, a polar group selected from the group consisting
of an ester group having at most 10 carbon atoms and an ether group
having at most 10 carbon atoms, or the aforesaid hydrocarbon
residue substituted with the polar group.
Practical examples of the aromatic norbornadiene derivatives are
1,4-dihydro-1,4-methano-naphthalene;
1,4-dihydro-1,4-methano-6-methylnaphthalene;
1,4-dihydro-1,4-methano-6-methoxycarbonylnaphthalene;
5,8-diacetoxy-1,4-dihydro-1,4-methanonaphthalene;
5,8-diacetoxy-6,7-dicyano-1,4-dihydro-1,4-methanonaphthalene;
5,8-diacetoxy-6,7-dimethyl-1,4-dihydro-6,7-dichloro-1,4-dihydro-1,4-methan
onaphthalene; 1,4-dihydro-1,4-methanoanthracene and
9,10-diacetoxy-1,4-dihydro-1,4methananthracene.
Other typical examples of the aromatic type norbornadiene
derivatives are described in the specification of Japanese Patent
Application Laid Open No. 61,500/'75.
Preferred cycloolefins are generally classified into monocyclic
monoolefinic compounds, nonconjugated cyclic polyene compounds, and
polycyclic olefinic compounds.
The monocyclic monoolefinic compounds are shown by the following
general formula (XXV) ##STR18## wherein n is an integer of 3 to
20.
Typical examples of the monocyclic monoolefinic compounds are
cyclopentene, cycloheptene, cyclooctene, cyclodecene,
cyclododecene, and those monocyclic monoolefinic compounds each
substituted by at least one hydrocarbon group selected from the
group consisting of an alkyl group having at most 10 carbon atoms,
an alkenyl group having at most 10 carbon atoms, and an aryl group
having at most 10 carbon atoms at the methylene carbon thereof.
Also, the nonconjugated cyclic polyene compounds are shown by the
following general formula (XXVI) and (XXVII) ##STR19## wherein l is
an integer of 1-20 and m and n each is an integer of 2-20.
Typical examples of the nonconjugated cyclic polyene compounds are
1,5-cyclooctadiene and 1,5,9-cyclododecatriene. Furthermore the
aforesaid nonconjugated cyclic polyene compounds substituted by at
least one of the aforesaid hydrocarbon groups and/or a halogen atom
may be used in this invention and typical examples of these
compounds are 1-chloro-1,5-cyclooctadiene and
1-methyl-1,5-cyclooctadiene.
Moreover, other examples of the nonconjugated cyclic polyene
compounds represented by aforesaid general formula (XXVII) are the
oligomers (generally having a polymerization degree of at most 100)
obtained by subjecting the cycloolefinic compounds represented by
the aforesaid general formula (XXV) or (XXVI) to, for example, a
metathesis polymerization.
Still further, the polycyclic olefinic compounds are the olefinic
compounds each having 2-10 rings and 1-5 carbon-carbon double
bonds.
Practical examples of the polylcyclic olefinic compounds are
bicyclo[2,2,1]-heptene-2 (i.e., norbornene);
5-methyl-bicyclo[2,2,1]-heptene-2;
5-vinyl-bicyclo[2,2,1]-heptene-2;
5-ethylidene-bicyclo[2,2,1]-heptene-2;
5-isopropenyl-bicyclo[2,2,1]-heptene-2; dicyclopentadiene;
bicyclo[2,2,1]-hepta-2,5-diene (i.e., norbornadiene); and
1,4,5,8-dimethano-1,2,3,4,4a,5,-8,8a-octahydronaphthalene.
The norbornene derivatives may each contain two or more polar
groups which are different from each other and in such norbornene
derivatives, at least two of the substituents W.sup.1, X.sup.1,
Y.sup.1 and Z.sup.1 in the above general formulae are polar groups
selected from the group consisting of cyano groups, ester groups,
halogen atoms (chlorine atom and bromine atom), ether groups, imide
groups, acid anhydride groups and amide groups or a hydrocarbon
residue substituted with these polar groups and the at least two
polar groups of the norbornene derivative differ from each other.
For example, in general formula (I), if W.sup.1 among W.sup.1,
X.sup.1, Y.sup.1 and Z.sup.1 is a cyano group, one of X.sup.1,
Y.sup.1 and Z.sup.1 is a different polar group than the cyano
group, such as an ester group, an ether group, and an amide group
or a hydrocarbon residue substituted with such a different polar
group.
In addition, there are two or more kinds of isomers, the endo type
isomer, the exo type isomer and other according to the positions of
the substituents in regard to the cyano type norbornene
derivatives, the ester type norbornene derivatives, the amide type
norbornene derivatives, the halogen type norbornene derivatives,
the acid anhydride type norbornene derivatives, the aromatic type
norbornene derivatives, the aromatic nitrogen-containing
heterocyclic type norbornene derivatives, the norbornene
derivatives having different polar groups, and some of the
cycloolefinic compounds (e.g., 5-methyl-bicyclo[2,2,1]-heptene-2)
among the above-described monomers. At the production of
ring-opening polymerization products, these isomers may be
separated before use by, for example, a rectifying method or a
recrystallization method but they may be used without being
separated or as a mixture of them.
The monomer of the type represented by general formula (I) may be
generally prepared by subjecting a corresponding compound having
one double bond (e.g., acrylonitrile, methyl methacrylate, vinyl
acetate, vinyl chloride, vinylidene chloride, styrene, etc.,) and
cyclopentadiene or dicyclopentadiene to a Diels-Alder reaction.
Also, the monomer of the type represented by general formula (III)
may be prepared similarly. In these reactions, the production
yields for the monomers of the type shown by general formula (I)
and general formula (III) depend upon the reaction conditions.
Furthermore, the monomer of the type represented by general formula
(III) is also obtained by subjecting the monomer of the type
represented by general formula (I) and cyclopentadiene or
dicyclopentadiene to a Diels-Alder reaction but in this case the
monomer of the type shown by general formula (I) sometimes remains
unreacted in the product. When the product is obtained as a mixture
of the monomer of the type of formula (I) and the monomer of
formula (III) in the aforesaid reactions, the monomers may be
separated from each other, if desired, by a rectifying method or a
recrystallization method. In the practice of this invention,
however, the monomers may be used as is (i.e., without
separation).
Furthermore, in general, as the content of the monomer of the type
represented by general formula (II) increases, the ring-opening
polymerization product having excellent heat resistance can be
obtained but, on the other hand, the polymer obtained has not
always sufficient workability or moldability.
Accordingly, in the case of carrying out the ring-opening
polymerization of the cyano type norbornene derivative, the ester
type norbornene derivative, the ether type norbornene derivative,
the halogen type norbornene derivative, the amide type norbornene
derivative, the aromatic norbornene derivative, or the aromatic
nitrogen-containing heterocyclic type norbornene derivative
indicated about, it is desirable to employ, respectively, the
monomer represented by formulae (I), (II), (VI), (XI), (IX), (XX)
or (XVIII) as the main component for the homopolymerization or
copolymerization. Moreover, in the ring-opening polymerization of
the imide type norbornene derivative, it is also preferred by the
same reason as above to employ the monomer shown by formula (XV) as
the main component for the homopolymerization or
copolymerization.
Furthermore, in the case of using as the starting materials for
producing ring-opening polymerization products of the cyano type
norbornene derivatives, the ester type norbornene derivatives, the
ether type norbornene derivatives, the halogen type norbornene
derivatives, the imide type norbornene derivatives, the amide type
norbornene derivatives, the aromatic type norbornene derivatives,
or the aromatic nitrogen-containing heterocyclic norbornene
derivatives among the aforesaid various monomers, the heat
resistance of the polymerization products decreases as the number
of carbon atoms of the monomers increases and hence it is
preferable that the monomers used have less than 40, particularly
less then 20 carbon atoms as the total carbon numbers (including
the carbons of the norbornene ring and the polar group or groups).
Also, in regard to the halogen type norbornene derivatives, the
number of the halogen atoms in said each derivative is at most
10.
In the preferred aromatic type norbornene derivatives, the aromatic
nucleus is phenyl or substituted phenyl. Furthermore, in the
aromatic nitrogen-containing heterocyclic norbornene derivatives,
it is desirable that the aromatic nitrogen-containing heterocyclic
group be a pyridyl group or a nucleus-substituted pyridyl group
having at most 10 carbon atoms.
Also, in regard to the acid anhydride norbornene derivatives, it is
preferred that the total carbon number thereof be at most 40 as in
the aforesaid cases and, in this case, it is more preferred that in
the monomers shown by formula (XIII) or (XIV), q is O and l and m
are 0 or 1, and the total carbon number is less than 20. In the
aromatic type norbornadiene derivatives, it is desirable that the
total carbon number be at most 40, in particular less than 20. In
particular, in general formula (XXIII) indicated above, it is
preferred that E.sup.1 and E.sup.4 are a hydrogen atom
or--OCOR.sup.25 (where, R.sup.25 has at most 5 carbon atoms) and
E.sup.2 and E.sup.3 are a hydrogen atom. Furthermore, in the ester
type norbornadiene derivatives, it is preferred that the total
carbon number be at most 40, particularly less than 30.
Therefore, in the case of ring-opening polymerizing at least one of
the cyano type norbornene derivatives, the ester type norbornene
derivatives, the ether type norbornene derivatives, the halogen
type norbornene derivatives, and the amide type norbornene
derivatives (other monomers than above may or may not be included
in the ring-opening polymerization or copolymerization), it is
preferred that the monomer represented by general formulae (I),
(II), (VI), (XI) and (IX), respectively, be present in the
polymerization system in an amount of at least 1 mole % in general,
more particularly more than 10 mole %, and particularly more than
50 mole %. Furthermore, in the case of ring-opening polymerizing
the imide type norbornene derivatives (other monomers than above
may or may not be included in the ring-opening polymerization or
copolymerization), it is preferred that the monomer of formula (XV)
be present in the polymerization system in an amount of generally
at least 1 mole %, more preferably more than 10 mole %, and
particularly more than 50 mole %. Still further, in the case of
ring-opening polymerizing the monomer represented by general
formula (XXIII), it is preferred that the monomer be present in an
amount of generally at least 1 mole %, more preferably more than 10
mole %, and particularly more than 50 mole %.
In the process of this invention, only one of these monomers may be
subjected to the ring-opening polymerization or two or more kinds
of the monomers may be subjected to the polymerization.
The organometallic compounds used for preparing the catalyst
systems used in this invention are the organometallic compounds
containing at least one of the metals belonging to Groups IA, IIA,
IIB, IIIB, IVA, and IVB of the periodic table and some of these
organometallic compounds are shown by the following formula
wherein M represents the metal belonging to Group IA, IIA, IIB,
IIB, IVA, or IVB of the periodic table; R.sup.26 represents an
organic group having at most 20 carbon atoms selected from an alkyl
group, an alkenyl group, an aryl group, an aralkyl group, an
alkoxide group, a phenoxy group, and a cyclopentadienyl group, a
hydrogen atom, or a halogen atom, the groups represented by
R.sup.26 may be the same or different and at least one of said
groups is a hydrogen atom or the organic group; n represents the
maximum atomic valence number of said metal or a positive integer
of less than the maximum atomic valence number.
Other examples of the organometallic compounds used in this
invention are the complexes of the aforesaid organometallic
compounds and an equimolar amount of pyridine, triphenylphosphine,
or diethyl ether; the reaction products of 1 mole of the aforesaid
organometallic compounds and at most 2.0 moles of water; and the
complex salts of two kinds of the aforesaid organometallic
compounds.
Typical examples of the organometallic compounds used in this
invention are the organometallic compounds of lithium, sodium,
potassium, magnesium, calcium, zinc, boron, aluminum, gallium,
titanium, zirconium, silicon, germanium, or tin. However, the
organometallic compounds of lithium, sodium, magnesium, zinc,
aluminum, or tin are preferable and further organoaluminum
compounds are particularly preferable. Practical examples of the
preferred organoaluminum compounds are triethylaluminum,
triisobutylaluminum, trihexylaluminum, diethylaluminum chloride,
di-n-butylaluminum chloride, ethylaluminum sesquichloride,
diethylaluminum butoxide, and the reaction product of
triethylaluminum and water at 1 : 0.5 by mole ratio. Other examples
of the organoaluminum compounds used in this invention are
described in the specifications of U.S. Pat. No. 3,856,758, and
Japanese Patent Application Laid Open Nos. 77,999/'74; 58,200/'75;
61,500/'75; 71,800/'75 and 75,300/'75. Still other examples of the
organoaluminum compounds are aluminum-siloxalane compounds,
aluminumamide compounds, dialumoxane compounds, and the double
salts containing these organoaluminum compounds.
The aforesaid aluminum-siloxalane compounds used as the
organometallic compounds in this invention are represented by the
following general formula (XXVIII) ##STR20## wherein R.sup.27
R.sup.28 and R.sup.29, which may be the same or different, each
represents a halogen atom, an alkyl group having at most 10 carbon
atoms, or an alkoxy group having at most 10 carbon atoms; R.sup.30
represents an alkyl group having at most 10 carbon atoms; and
R.sup.31 represents an alkyl group having at most 10 carbon atoms,
an alkoxy group having at most 10 carbon atoms, or a substituent
having the general formula (XXIX) ##STR21## (where, R.sup.32,
R.sup.30 and R.sup.34, which may be the same or different, each has
the same meaning as with R.sup.27, R.sup.28, and R.sup.29 above and
n is a positive integer less than 10).
Practical examples of the aluminum-siloxalane compounds used in
this invention are dimethylaluminum-trimethylsiloxalane,
diethylaluminum-trimethylsiloxalane,
di-n-propylaluminum-trimethylsiloxalane,
diisobutylaluminum-trimethylsiloxalane,
dioctylaluminum-trimethylsiloxalane,
dimethylaluminum-trichlorosiloxalane,
diethylaluminum-dimethylethylsiloxalane,
dimethylaluminum-trimethoxysiloxalane,
dimethylaluminum-triethylsiloxalane,
dimethoxyaluminum-trimethylsiloxalane ,
dimethoxyaluminum-trimethylsiloxalane, and
dichloroaluminum-trimethoxysiloxalane.
Also, the aluminum amide compounds used as the organometallic
compounds in this invention are shown by the following general
formula (XXX) ##STR22## wherein R.sup.5, R.sup.6 and R.sup.7 which
may be the same or different, each represents a hydrogen atom or an
alkyl group having at most 10 carbon atoms and R.sup.8 represents a
halogen atom or an alkyl group having a most 10 carbon atoms.
Practical examples of the aluminum amide compounds used in this
invention are diethylaluminum dimethylamide, diethylaluminum
diethylamide, dimethylaluminum dimethylamide, dimethylaluminum
di-n-butylamide, diethylaluminum di-n-butylamide, dichloroaluminum
dimethylbutylamide, dimethylaluminum dioctylamide,
diisobutylaluminum di-n-butylamide, and dihexylalumium
dioctylamide.
The dialumoxane compounds used as the organometallic compounds in
this invention are shown by the following general formula (XXXI)
##STR23## wherein R.sup.9, R.sup.40 and R.sup.41, which may be the
same or different, each represents a halogen atom, an alkyl group
having at most 10 carbon atoms, or an alkoxy group having at most
10 carbon atoms and R.sup.42 represents an alkyl group having at
most 10 carbon atoms.
Practical examples of the dialumoxane compounds used in this
invention are tetramethyl dialumoxane, tetraethyl dialumoxane,
tetraisobutyl dialumoxane, 1,1-dimethyl-3,3-diethyl dialumoxane,
1,1-dimethyl-3,3-diisobutyl dialumoxane, tetradecyl dialumoxane,
trimethyl dialumoxane chloride, and triethyl dialumoxane
chloride.
Furthermore, typical and practical examples of the organometallic
compounds other than the organoaluminum compounds are
n-butyllithium, phenyllithium, n-amylsodium,
cyclopentadienylsodium, phenylpotassium, diethylmagnesium,
ethylmagnesium chloride, methylmagnesium iodide, allylmagnesium
chloride, n-propylmagnesium chloride, tert-butyl magnesium
chloride, phenylmagnesium chloride, diphenylmagnesium, ethyl
ethoxymagnesium, dimethylzinc, diethylzinc, diethoxyzinc,
phenylcalcium iodide, dibutylboron chloride, diborane,
trimethylboron, triethylsilane, silicon tetrahydride, triethyl
silicon hydride, dimethylgallium chloride, titanium tetrahydride,
titanium tetra-n-butoxide, dicyclopentadienytitanium dichloride,
dicyclopentadienyl zirconium dichloride, tetramethyltin,
tetraethyltin, trimethyltin chloride, dimethyltin dichloride,
trimethyltin hydride, tetraethoxytin, tetrabutoxytin, a complex of
ethylmagnesium- bromide and ethanol, and the reaction product of
diethylzinc and water (H.sub.2 O/Zn(C.sub.2 H.sub.5).sub.2 < 2.0
by mole ratio).
Other examples of the organometallic compounds used in this
invention are the double salts of two kinds of the aforesaid
organometallic compounds such as, for example, lithium aluminum
tetrahydride, calcium tetraethylzinc, etc.
In the practice of this invention, the above-mentioned
organometallic compounds may be used individually or as a mixture
of two or more of these compounds.
The reaction product of the oxide and a phosphorus pentahalide or
phosphorus oxytrihalide used for preparing the catalyst system in
this invention can be prepared by reacting the oxide (i.e.,
tungsten oxide and/or molybdenum oxide) and a phosphorus
pentahalide or phosphorus oxytrichloride in the presence or absence
of an inert organic solvent.
Typical examples of the oxides used in the above reaction are
tungsten trioxide, molybdenum trioxide, and tungsten or molybdenum
oxyhalide such as, tungsten dioxydichloride, tungsten
oxytetrachloride, and molybdenum oxytrichloride. Tungsten trioxide
and molybdenum trioxide are particularly preferable.
Typical examples of phosphorus pentahalide and phosphorus
oxytrihalide are phosphorus pentachloride, phosphorus
pentafluoride, phosphorus pentabromide, phosphorus pentaiodide and
phosphorus oxytrichloride. Phosphorus pentachloride is particularly
preferable.
In the case of producing the reaction product, the ratio of the
phosphorus compound to 1 mole of the oxide is generally 0.01 to 100
moles, preferably 0.05 to 50 moles, and most preferably 0.1 to 20
moles. If less than 0.01 mole or more than 100 moles of the
phosphorus compound is reacted per mole of the oxide, a large
amount of unreacted oxide or phosphorus compound remains in the
reaction system, which does not contribute to increase the
catalytic activity of the catalyst.
Also, the reaction temperature employed in the above reaction is
generally 0.degree. to 300.degree. C, preferably 40.degree. to
260.degree. C, particularly 60.degree. to 220.degree. C. If the
reaction temperature is lower than 0.degree. C, the rate of
reaction is low, while if the reaction temperature is higher than
300.degree. C, it does not contribute to further increase the
polymerization activity.
The reaction preferably is carried out in an inert organic solvent
and the inert organic solvent means an organic solvent which does
not cause a reaction with the aforesaid oxide and the phosphorous
compound and is in a liquid state at the reaction temperature. It
is preferred that the solvent have a melting point of lower than
30.degree. C., more preferably lower than 20.degree. C., and more
particularly lower than 10.degree. C. and a boiling point of lower
than 500.degree. C., more preferably lower than 400.degree. C., and
particularly lower than 300.degree. C.
Examples of the inert organic solvents are aliphatic hydrocarbons
such as pentane, hexane, heptane, octane, and decane; alicyclic
hydrocarbons such as cyclopentane and cyclohexane; aromatic
hydrocarbons such as benzene, toluene, and xylene; halogenated
hydrocarbons such as methylene chloride, ethyl chloride,
1,1-dichloroethane, 1,2-dichloroethane, 1,2-dichloroethylene,
1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane,
1-chloro-2-methylpropane, 1-chloropentane, chlorobenzene,
o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene; and
ethers such as diethyl ether and tetrahydrofuran.
At the production of the reaction product of the oxide and the
phosphorus compound, the ratio of the inert organic solvents to the
oxide employed depends upon the reaction conditions but is
generally less than 50 parts by weight, preferably less than 29
parts by weight per one part by weight of the oxide. Even if more
than 50 parts of inert organic solvents are used, it does not
contribute to increase further the catalytic activity, which makes
the use of such a large amount of the inert organic solvents
meaningless.
In the above-mentioned reaction of producing the reaction product
of the oxide and the phosphorus compound, the inert organic
solvents described above may be used individually or as a mixture
of them. Furthermore, the oxides and the phosphorus compounds
described above each may be used individually or as a mixture of
them respectively.
In a preferred embodiment of the aforesaid reaction, the reaction
is carried out under the above-indicated reaction conditions such
as the preferred reaction component ratio and reaction temperature
and then the supernatant liquid formed is used as the catalyst
component. When the reaction product of the oxide and the
phosphorus compound prepared by such a method is used for preparing
the catalyst system, the catalyst system shows quite high catalytic
activity.
The period of time required for finishing the above-mentioned
reaction depends upon the reaction temperature and the ratio of the
phosphorus compound to the oxide in the reaction system but is
generally from a few minutes to a few hours. The reaction is
finished when the supernatant liquid becomes red-purple or dark red
and by using the catalyst system prepared using the reaction
product (in particular, the supernatant liquid) having the
aforesaid color, the ring-opening polymerization can be practiced
at a high polymerization activity.
In addition, when a supernatant or a filtrate recovered from a
solution containing the reaction product of the oxide and the
phosphorus compound prepared by the aforesaid method is used, a
homogeneous catalyst system is obtained but the aforesaid solution
of the reaction product together with insoluble matters can be also
used effectively for preparing the catalyst system without causing
any troubles.
In the catalyst system prepared from the aforesaid reaction product
of the oxide and phosphorus compound and the aforesaid
organometallic compound, it is preferred that the ratio of the
organometallic compound to 1 atom equivalent of tungsten and/or
molybdenum contained in the reaction product is 0.1 - 100 moles,
more preferably 0.3 - 40 moles, and particularly 0.5 - 20 moles. If
the proportion of the organometallic compound is less than 0.1 mole
per 1 atom equivalent of tungsten and/or molybdenum in the reaction
product, the catalyst system prepared does not show sufficient
catalytic activity, while if the proportion of the organometallic
compound is higher than 100 moles, no further improvement of the
catalytic activity is obtained.
In the practice of this invention, the catalytic system obtained
from the above-mentioned organometallic compound and the reaction
product of the oxide and the phosphorus compound can be effectively
used but the catalyst system used in this invention may further
contain a third component or third components.
Examples of such third components are water, oxygen,
oxygencontaining organic compounds, nitrogen-containing organic
compounds, halogen-containing organic compounds,
phosphoruscontaining organic compounds, sulfur-containing organic
compounds, metal salts of a carboxylic acid, metal hydroxides,
metal oxides, metal halides, metal chelate compounds, metal
alkoxides and phenoxides, metal salts and reactive group-containing
polymers.
The oxygen-containing organic compounds have less than 30 carbon
atoms, preferably 20 or less than 20 carbon atoms. Typical examples
of these oxygen-containing organic compounds are peroxides such as
an alkyl peroxide (e.g., tert-butyl peroxide), an aryl peroxide
(e.g., benzoyl peroxide), an alkyl hydroperoxide (e.g., tert-butyl
hydroperoxide), an aralkyl hydroperoxide (e.g., cumene
hydroperoxide), a peracid (e.g., peracetic acid), and the esters,
ketones, and aldehydes of them; epoxide compounds such as ethylene
oxide, butene-1-oxide, epichlorohydrin, allylglycidyl ether, and
butadiene monooxide; acetal compounds such as acetaldehyde diethyl
acetal, 1,1-diethoxydiethane, and dichloroacetaldehyde dimethyl
acetal; orthocarboxylic acid esters such as orthoformic acid alkyl
ester (e.g., orthoformic acid methyl ester); alcohol compounds such
as a monohydric alcohol (e.g., methanol, ethanol, n-butyl alcohol,
and isobutyl alcohol), a phenolic compound (e.g., phenol), and
polyhydric alcohol (e.g., ethylene glycol, propylene glycol,
tetramethylene glycol, glycerine, xylylene glycol, and
1,4-cyclohexane diol); carboxylic acids such as an aliphatic
monohydric carboxylic acid having at most 20 carbon atoms (e.g.,
formic acid, acetic acid, propionic acid, butyric acid, and capric
acid), an aromatic or alicyclic monohydric carboxylic acid (e.g.,
benzoic acid and cyclohexane carboxylic acid) and a polyhydric
carboxylic acid having at most 20 carbon atoms (e.g., succinic
acid, fumaric acid, maleic acid, glutaric acid, sebacic acid, and
1,4-cyclohexanedicarboxylic acid); carboxylic acid anhydrides such
as the anhydride of an aromatic or aliphatic monohydric carboxylic
acid having at most 20 carbon atoms (e.g., acetic anhydride,
propionic anhydride, butyric anhydride, and benzoic anhydride) and
the anhydride of a cyclic acid (e.g., maleic anhydride, citraconic
anhydride, bicyclo[2,2,1]-hepta-2-ene-5,6-dicarboxylic anhydride,
and hexahydrophthalic anhydride); carboxylic acid ester compounds
such as a carboxylic acid ester of a mono to trihydric carboxylic
acid having at most 20 carbon atoms and a monohydric alcohol or
phenol having at most 20 carbon atoms (e.g., ethyl formate, methyl
acetate, methyl caproate, ethyl benzoate, dimethyl succinate, ethyl
glutarate, ethyl cebacate, and dimethyl terephthalate), a cyclic
ester (e.g., .gamma.-butyrolactone and .epsilon.-caprolactone), and
carboxylic acid ester compounds such as a carboxylic acid ester of
a mono to trihydric hydroxy compound having at most 20 carbon atoms
(e.g., an ester of an alcohol or phenol) and a monohydric
carboxylic acid; carbonate compounds such as a carbonate of a
monohydric hydroxy compound (e.g., diethyl carbonate, di-n-propyl
carbonate, and diphenyl carbonate) and a tetraalkyl orthocarbonate
(eg., tetramethyl orthocarbonate and tetra-n-butyl orthocarbonate);
ketone compounds such as acetone, methyl ethyl ketone, and
cyclopentanone; and ether compounds such as diethyl ether,
di-n-butyl ether, anisole, and diphenyl ether.
The nitrogen-containing organic compounds have less than 40 carbon
atoms, preferably 30 or less than 30 carbon atoms, and most
preferably 20 or less than 20 carbon atoms. As such nitrogen
containing organic compounds, there are illustrated amine
compounds, nitrogen-containing heterocyclic compounds, acid amide
compounds, compounds having a nitrogen-oxygen bond, and compounds
having a nitrogen-halogen bond.
Examples of the amine compounds are primary amines such as
methylamine, ethylamine, isopropylamine, n-butylamine,
cyclohexylamine, benzylamine, aniline, and naphthylamine; secondary
amines such as dimethylamine, methylethylamine,
N-methylcyclohexylamine, N-methylbenzylamine, N-methylaniline,
pyrrolidine, diethylamine, dicyclohexylamine, dibenzylamine, and
di-n-propylamine; tertiary amines such as triethylamine,
tri-n-butyamine, methyl-di-n-butylamine,
N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine,
N,N-dimethylaniline, and N-ethylpyrrolidine; diamines such as
ethylenediamine, trimethylenediamine, hexamethylenediamine,
1,4-cyclohexanediamine, p-phenylenediamine, N,N-dimethylenediamine,
N,N-dimethylhexamethylenediamine, piperazine,
N,N,N',N'-tetramethylethylenediamine, and
N,N,N'-N'-tetramethyl-p-phenylenediamine; and the N-hydrocarbon
substitution derivatives of them.
Examples of the nitrogen-containing heterocyclic compounds are
pyridine and the alkyl-substituted derivatives of it such as
.alpha.-, .beta.-, or .gamma.-picoline, 2,3-lutidine- 2,4-lutidine,
2,5-lutidine, 2,6-lutidine, 3,4-lutidine, 2,5-lutidine,
2,3,6-collidine and 2,4,6-collidine and quinoline and the
alkyl-substituted derivatives of it such as 2-methylquinone,
4-methylquionline, 6-methylquinoline, 7-methylquinoline,
8-methylquinoline, isoquinoline, and 1-methyl isoquinoline.
The acid amide compounds are carboxylic acid amide compounds of
monohydric or polyhydric carboxylic acids and ammonia or a primary
or secondary amine such as acetamide, propionamide, hexaneamide,
cyclohexane carbonamide, benzamide, N-methylacetamide,
N-methylbenzacetoanilide, N,N-dimethyl formamide,
N-methylacetanilide, succinamide, adiamide, and maleinamide; cyclic
amide compounds such as -butyrolactam and -caprolactam; urea and
derivatives of it such as 1,1-dimethylurea, 1,3-dimethylurea,
1,3-di-n-butylthiourea, and tetramethylurea; sulfonamides such as
benzensulfonamide and p-toluenesulfonamide; and
hexamethylphosphorus triamide.
Examples of the compounds having a nitrogen-oxygen bond are
N-nitroso compounds and o-nitroso compounds such as
N-nitrosodimethylamine, N-nitroso-N-methylphenylamine,
N-nitrosodiphenylamine, n-amylnitrite, and isoamyl nitrite and
aliphatic nitro compounds and aromatic nitro compounds (nitroaryl)
having 1-3 nitro groups and 0 - 4 chlorine atoms such as
nitroethane, 4-chloro-1-nitrotoluene, dinitrophenol,
4-chloro-2-nitroanisole, 1,3-dinitrobenzene, amyl nitrate and
1,2-dinitro-3,5-dichlorobenzene.
Furthermore, examples of the compounds having a nitrogenhalogen
bond are trichloromelamine, N-chlorosuccinimide,
N-bromosuccinimide, N-chlorophthalimide, and
N-bromophthalimide.
The halogen-containing organic compounds have less than 20 carbon
atoms and examples of the halogen-containing organic compounds are
aliphatic hydrocarbons having one or two or more carbon-carbon
double bonds, at least one carbon of said double bond having been
substituted by a halogen atom, such as vinyl chloride; vinylidene
chloride, trichloroethylene, tetrachloroethylene, chloroprene, and
hexachloro-cyclopentadiene; halogenated aromatic hydrocarbons such
as chlorobenzene, bromobenzene, and dichlorobenzene; tertiary
hypohalide compounds; allylhalide compounds such as allyl chloride;
tertiary alkylhalide compounds such as tert-butyl chloride;
halogenated ketone compounds such as .alpha.-chloroacetone; and
halogenated alcohol compounds such as 2-chloroethanol.
The phosphorus-containing organic compounds have less than 30
carbon atoms and examples of them are phosphine compounds such as
tri-n-butylphosphine and triphenylphosphine; phosphine oxide
compounds such as tri-n-butylphosphine oxide and triphenylphosphine
oxide; phosphite compounds such as trimethyl phosphite, triethyl
phosphite, and triphenyl phosphite; phosphate compounds sush as
trimethyl phosphate, tri-n-butyl phosphate, and triphenyl
phosphate; compounds having phosphorus-chlorine bond such as
dichlorophenyl and chlorodiphenyl phosphines; and halogencontaining
phosphate compounds represented by the formula
wherein R.sup.43, R.sup.44 and R.sup.45, which may be the same or
different, each represents a hydrocarbon group having at most 20
carbon atoms, at least one of said R.sup.43, R.sup.44 and R.sup.45
being a hydrocarbon residue substituted with at least one halogen
atom.
Typical examples of the halogen-containing phosphate compounds are
selected from the group consisting of tris (.beta.-chloro-ethyl)
phosphate, tris (.beta.-bromoethyl) phosphate, tris
(2,3-dichloro-n-propyl) phosphate, tris (2,3-dibromo-n-propyl)
phosphate, tris (2-bromo-3-chloro-n-propyl) phosphate, tris
(3-chloro-n-propyl) phosphate, tris(dichloro-isopropyl)phosphate
and tris (2,4-dichloro-phenyl)phosphate.
Sulfur-containing organic compounds have less than 20 carbon atoms
and examples of them are sulfide compounds such as diethyl sulfide,
di-n-butyl sulfide, methylphenyl sulfide, diphenyl sulfide, and
thiophene; sulfoxide compounds such as dimethyl sulfoxide,
tetramethylene sulfoxide, and di-n-butyl sulfoxide; sulfone
compounds such as dimethylsulfone, di-n-propylsulfone,
tetramethylenesulfone, and diphenylsulfone; and compounds having a
sulfur-halogen bond such as phenylsulfenyl chloride chloride and
2,4 -dinitrophenylsulfenyl chloride.
The metal salts of a carboxylic acid have at most 30 carbon atoms
and examples of these compounds are the metal salts of a saturated
monohydric carboxylic acid having 2 - 30 carbon atoms, such as
propionic acid, 2-ethylhexanoic acid, palmitic acid, heptadecanoic
acid, and nonadecanoic acid and a metal such as lithium, sodium,
magnesium, calcium, barium, aluminum, lead, cobalt, and nickel; the
metal salts of a saturated carboxylic acid containing a cycloalkyl
group having 6 - 30 carbon atoms or a substituted cycloalkyl group
and the aforesaid metals; and the metal salts of a carboxylic acid
containing a phenyl or a substituted phenyl group and the aforesaid
metals.
The metal oxides are the oxides of the metals belonging to Groups
IA, IB, IIA, IIB, IIIA, IIIB, IVA. IVB, VA, VB, VIA, VIB, VIIA and
VIIIA of the periodic table and also include the double oxides
containing two or more of the aforesaid metals and the peroxides of
the aforesaid metals.
Examples of the metal oxides are lithium oxide, sodium oxide,
potassium oxide, rubidium oxide (Rb.sub.2 O, RbO.sub.2,RbO), cesium
oxide (Cs.sub.2 O, CsO.sub.2, Cs.sub.2 O.sub.3), copper oxide (CuO,
Cu.sub.2 0), silver oxide, beryllium oxide, magnesium oxide,
calcium oxide, strontium oxide, barium oxide (BaO, BaO.sub.2), zinc
oxide, cadmium oxide (CdO, CdO.sub.2), mercury oxide (HgO, Hg.sub.2
O), scandium oxide, cerium oxide (Ce.sub.2 O.sub.3, CeO.sub.2,
CeO), boron oxide (BO, B.sub.2 O.sub.3), aluminum oxide, gallium
oxide (Ga.sub.2 O, Ga.sub.2 O.sub.3), indium oxide (In.sub.2 O,
InO, In.sub.2 O.sub.3), titanium oxide (Ti.sub.2 O.sub.3,
TiO.sub.2), zirconium oxide, hafnium oxide, silicon oxide,
germanium oxide (GeO, GeO.sub.2), tin oxide (SnO, SnO.sub.2), lead
oxide (PbO, Pb.sub.3 O.sub.4, Pb.sub.2 O.sub.3, PbO.sub.2),
vanadium oxide (V.sub.2 O.sub.2, V.sub.2 O.sub.3, V.sub.2 O.sub.4,
V.sub.2 O.sub.5), niobium oxide, tantalum oxide, antimony oxide
(Sb.sub.2 O.sub.3, Sb.sub.2 O.sub.4, Sb.sub.2 O.sub.5 ), bismuth
oxide (Bi.sub.2 O.sub.3, Bi.sub.2 O.sub.5), chromium oxide (CrO,
Cr.sub.2 O.sub.3, CrO.sub.3), molybdenum oxide (MoO.sub.2,
MoO.sub.3), tungsten oxide (Wo.sub.2, WO.sub.3), selenium oxide,
tellurium oxide (TeO.sub.2, TeO.sub.3), manganese oxide (MnO,
Mn.sub.3 O.sub.4, MnO.sub.2, MnO.sub.3, Mn.sub.2 O.sub.7), rhenium
oxide (ReO.sub.2, Re.sub.2 O.sub.7), iron oxide (FeO, Fe.sub.3
O.sub.4, Fe.sub.2 O.sub.3), cobalt oxide (CoO, Co.sub.3 O.sub.4,
Co.sub.2 O.sub.3), nickel oxide (NiO, Ni.sub.3 O.sub.4, Ni.sub.2
O.sub.3), ruthenium oxide (Ru.sub.2 O.sub.3, RuO.sub.2, RuO.sub.4),
rhodium oxide (Rh.sub.2 O.sub.3, RhO.sub.2), osmium oxide
(OsO.sub.2, OsO.sub.4), iridium oxide and platinum oxide (PtO,
PtO.sub.2). Further, as the double oxides there are exemplied
titaniferous iron ore (FeTiO.sub.3), CaTiO.sub.3, SiO.sub.2
-Al.sub.2 O.sub.3 and SiO.sub.2 -Cr.sub.2 O.sub.3.
The metal oxide may be used alone or as a mixture of two or more
thereof. The metal oxides may contain water of crystallization and
in a certain case the catalyst system prepared from the metal oxide
containing the water of crystalization possesses a higher
polymerization activity.
The metal hydroxides are the hydroxides of the metals belonging to
Groups IA, IV, IIA, IIB, IIIB, IVA, IVB, VB, VIIA and VIII of the
periodic table and also include the double salts of the metal
hydroxides and the carbonate of aforesaid metals.
Examples of the metal hydroxides are lithium hydroxide, sodium
hydroxide, potassium hydroxide, magnesium hydroxide, calcium
hydroxide, strontium hydroxide, barium hydroxide, zinc hydroxide,
cupric hydroxide, aluminum hydroxide, titanium hydroxide, stannic
hydroxide, lead (IV) hydroxide, bismuth hydroxide, manganese,
hydroxide, ferrous hydroxide, ferric hydroxide, nickel (I)
hydroxide, nickel (II) hydroxide, cobalt (II) hydroxide and cobalt
(III) hydroxide. The double salts of the hydroxide are basic lead
carbonate [PbCO.sub.3 .multidot.Pb(OH).sub.2 ], basic copper
carbonate [CuCO.sub.3 .multidot.Cu(OH).sub.2 ], basic magnesium
carbonate [(Mg.sub.4 (OH).sub.2 .multidot.(CO.sub.3).sub.3 ]and
basic cobalt carbonate [Co.sub.5 (0H).sub.6
.multidot.(CO.sub.3).sub.2 ]. The metal hydroxide may be used alone
or as a mixture of two or more thereof.
The metal halides are the halides, oxyhalides and hydroxyhlides of
the metals belonging to the Groups IA, IB, IIA, IIB, IIIA, IIIB,
IVA, IVB, VA, VB, VIA, VIB, VIIA, and VIII of the periodic
table.
Examples of the chlorides among the metal halides are LiCl, NaCl,
KCl, CuCl.sub.2, BeCl.sub.2, MgCl.sub.2, CaCl.sub.2, SrCl.sub.2,
BaCl.sub.2, ZnCl.sub.2, HgCl, HgCl.sub.2, BCl.sub.3, AlCl.sub.3,
TiCl.sub.3, TiCl.sub.4, ZrCl.sub.4, SiCl.sub.4, SnCl.sub.2,
SnCl.sub.4, PbCl.sub.2, VCl.sub.3, SbCl.sub.3, SbCl.sub.5,
MnCl.sub.2, FeCl.sub.2, FeCl.sub.3, CoCl.sub.2 and NiCl.sub.2.
Also, the fluorides, bromides and iodides in which a chlorine atom
in the aforesaid chlorides is replaced by a fluorine, bromine or
iodine are other typical examples.
Furthermore, the metal oxyhalide is VoCl.sub.3. The metal
hydroxyhalide is magnesium hydroxychloride. Besides, the double
salts of these metal halides, metal oxyhalides and hydroxyhalides
may be used in this invention.
There are anhydride and an hydrate among the metal halides but each
of them may be used. However, it is desirable to use the anhydride
because of its high polymerization activity.
The metal chelate compounds are the chelate compounds of the metals
belonging to Groups IA, IB, IIA, IIB, III, IVA, IVB, VA, VB, VIA,
VIIA, and VIII of the periodic table. The typical examples of the
metal chelate compounds are the chelate compounds of the aforesaid
metals and dibasic carboxylic acid, natural aminoacid, aminoacid
(not present in nature), oxyacid, polyphosphoric acid,
nitrocarboxylic acid, other acids, salts thereof, aliphatic amine,
aromatic amine, peptide, salicyclic aldehyde, derivatives thereof,
other oxyaldehyde, .beta.-diketone, phenol derivatives and o,
o'-dioxyazo dyestuff and the like, and also they are described in
the "Metal Chelate Compound" by E.M. artel M. Calvin.
The typical examples are the chelate compounds which include
acetylacetone, salts thereof, ethylenediamine, polyphosphoric acid,
ethylenediamine tetraacetic acid, salts thereof, dipyridyl,
triethylenetetramine, citric acid, its salts, salicylic aldehyde,
8-oxyquinoline, pyrophosphoric acid, its salts, nitroaceticacid,
cysteine, ammonium tri-acetic acid, 4,4'-diaminodiphenyl ether,
o-diaminobenzene, 2,4:dihydroxybenzoic acid, o-nitrophenol and
Eriochrome Black-T as a ligand.
The metal alkoxides and phenoxides are those of the metal belonging
to the Groups IA, IIA, IIB, IIIB, IVA, IVB, VA, VIA, VIIA and VIII
of the periodic table and alkoxides and phenoxides having at most
30 carbon atoms and a compound having at least one alkoxy or
phenoxy group.
Examples of the metal alkoxides and phenoxides are lithium
isoproside, sodium ethoxide, magnesium diethoxide, barium
diethoxide, zinc diethoxide, boron triisoproxide, aluminum
isopropoxide, gallium trimethoxide, silicon tetraethoxide titanium
tetraisopropoxide, tungsten hexaisopropoxide, manganese diethoxide,
iron triethoxide, magnesium diphenoxide, monoethoxy magnesium
chloride, triethoxy zirconium chloride and triethoxy vanadate.
The metal salts are those of metals belonging to the Groups IA, IB,
IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIIA and VIII of the
periodic table, rare earth elements and radioactive elements and
sulfates (including bisulfates, oxysulfates, double salts of
ammonium sulfate and metal sulfate and double salts of these
sulfates), sulfites (including bisulfites), thiosulfates,
phosphates (including hydrogen phosphates, double salts of ammonium
phosphates and metal phosphates and double salts of these
phosphates), phosphites (including metaphosphates), carbonates,
bicarbonates, nitrates, nitrites (including double salts of the
nitrates), cyanides and thiocyanides.
Examples of the metal salts are magnesium sulfate, stannous
sulfate, ferrous ammonium sulfate, aluminum sodium sulfate,
titanium oxysulfate, vanadium oxysulfate, sodium sulfite, silver
sulfite, potassium bisulfite, sodium thiosulfate, sodium
phosdihydron phosphate, potassium phosphite, nickel carbonate,
potassium bicarbonate, chromium nitrate, barium nitrate, silver
cyanate, mercury cyanide and cuprothiocyanide. The metal salts may
contain water of crystallization.
The reactive group-containing polymers whose molecular chain
contains at least one reactive group include a polymer containing a
hydroxyl group, a polymer containing a carboxyl group, a polymer
containing an ester group, a polymer containing an acid amide
group, a polymer containing an amino group, a polymer containing an
isocyanato group, a polymer containing a nitrile group, a polymer
containing an acid halogen group, a polymer containing an
oxygen-bearing heterocyclic ring, a polymer containing a
sulfur-bearing heterocyclic ring, a polymer containing a
nitrogen-bearing heterocyclic ring, a polymer containing a peptide
group, a polymer containing a thiol group, a polymer containing a
carbonyl group, and a polymer consisting of a sulfurbearing vinyl
compound. It is known that these polymers are molded into various
articles of use as an adhesive or coating agent. The method of this
invention further permits the use of stereospecific,
nonsterospecific or block copolymers obtained by using a monomer
containing a reactive group. Graft polymers formed by grafting a
compound containing a reactive group to polymers free from a
reactive group such as polyethylene, polypropylene and polystyrene
or polymers modified by a compound containing a reactive group are
also included in this invention. It is desirable to use the
polymers whose molecular chain contains at least one reactive group
which generally have a degree of polymerization of 30 to 10000,
preferably 100 to 700 and also have at least 10 reactive groups per
1000 carbons of its main chain in view of its polymerization
activity.
Examples of these polymers are described in the specification of
Japanese Patent Application Laid Open No. 53672/74.
When the aforesaid third component is used as a part of the
catalyst system in this invention, the proportion thereof depends
on the kind used but it is generally less than 50 moles, usually
less than 30 moles per atom equivalent of tungsten and/or
molybdenum contained in the catalyst. If the third component is
used in an amount larger than 50 moles per atom equivalent of the
metal component, it does not further increase the polymerization
activity of the catalyst.
The amount of the catalyst system used in the ring-opening
polymerization of this invention depends upon the kind of catalyst
and the kind of monomer used but in general it is preferably that
the number of gram atoms of tungsten and/or molybdenum is 0.001 -
100, more preferably 0.005 - 50, and particularly 0.01 - 10 per
1000 moles of the number of monomer. If the gram atoms of the metal
is less than 0.001 per 1000 moles of the monomer, the catalyst does
not show sufficient polymerization activity. On the other hand, if
the atom equivalents of metal are higher than 100 per 1000 moles of
the monomer, the removal of the catalyst after polymerization
becomes difficult and also the polymer obtained is greatly
colored.
In the present invention, the aforesaid monomer may be subjected to
ring-opening polymerization using the catalyst system prepared from
the above-mentioned organometallic compound and the reaction
product of the oxide and the phosphorus compound or these compounds
and the aforesaid third components in the absence of an inert
organic solvent (that is, a bulk polymerization), but the
ring-opening polymerization may be carried out in an inert organic
solvent. It is as a matter of course required that the organic
solvent used in the polymerization does not injure the catalyst
system and does not cause reaction with the monomer or monomers
used in this invention. It is particularly preferable to use as the
solvent the inert organic solvent as used in the production of the
reaction product of the oxide and the phosphorus compound. Thus,
typical examples of the inert organic solvent are those illustrated
in the case of showing the inert organic solvent used for producing
the reaction products of the oxides and the phosphorus compounds.
The organic solvents may be used individually or as a mixture of
them.
When the ring-opening polymerization is carried out in the
above-described inert organic solvent, the proportion of the
organic solvent is generally at most 20 volume parts, preferably 10
volume parts per volume part of the monomer or monomers. If the
porportion of the solvent is higher than 20 volume parts per volume
part of the monomer, it becomes troublesome to recover the
ring-opening polymerization product obtained after the
polymerization is finished. Furthermore, the recovery of the
organic solvent used is also troublesome.
The polymerization temperature is generally from -100.degree. to
200.degree. C., preferably from -50.degree. to 150.degree. C., and
most preferably from 0.degree. to 130.degree. C. If the
polymerization temperature is lower than -100.degree. C., the rate
of polymerization is quite low owing to the insufficient
polymerization activity in the polymerization system and thus it
requires a long period of time to finish the ring-opening
polymerization. In this case, further, the mixture of the monomer
and the aforesaid inert organic solvent, is as the case may be,
solidified. On the other hand, if the polymerization temperature is
higher than 200.degree. C., it becomes sometimes difficult to
control sufficiently the polymerization.
It is preferred to carry out the ring-opening polymerization of
this invention in an inert gas atmosphere such as argon and
nitrogen. If the oxygen and moisture are present in the
polymerization system, the catalyst system is partially or wholely
degraded, which makes it impossible to obtain reproducible
results.
By carrying out the ring-opening polymerization in the manner as
described above, the desired ring-opening polymerization products
can be obtained and in this case, the molecular weight of the
ring-opening polymerization products obtained can be controlled
properly by adding to the polymerization system a molecular weight
controlling agent such as .alpha.-olefins having at most 15 carbom
atoms (e.g., ethylene, propylene, butene-1, hexene-1, and
octene-1); internal olefins having at most 20 carbon atoms (e.g.,
butene-2, hexene-2, and octene-2); conjugated diolefins having at
most 20 carbon atoms and the halogen-substituted conjugated
diolefins (e.g., butadiene, isoprene, and chloroprene); and
non-conjugated diolefins having at most 20 carbon atoms (e.g.,
1,4-hexadiene). Other examples of the molecular weight controlling
agents are acetylene compounds having at most 20 carbons atoms such
as 1-pentyne, 2-pentyne, 3-methyl-1-butyne 1-hexane,
1-butylacetylene, 1-heptyne, 3-octyne, 1-decyne, vinylacetylene,
1,5-hexa-diine, 1,8-nona-diine, and 1,9-deca-diine, allene
compounds having at most 20 carbon atoms such as allene,
methylallene, ethylallene, trimethylallene, and tetramethylallene,
triolefin compounds having at most 20 carbon atoms such as 1,3,5-
heptatriene, 1,3,5-octatriene, 1,3,5,7-octatetriene, 3-methyl-1,3,5
heptatriene, 3,4-dimethyl-1,3,5-heptatriene, and 1,3,6-octatriene,
allyl compounds having at most 20 carbon atoms such as allyl
alcohol, allyl ether, allylethyl ether, allylphenyl ether,
allylamine, diallylamine, allyl chloride, allyl methacrylate,
diallyl oxalate, diallyl malonate, and diallyl phthalate, as
described in the specifications of Japanese Patent Application Laid
Open Nos. 56,494/'75; 56,495/'75; 56,496/'75; and 56,497/'75.
In the case of using the molecular weight controlling agent, the
proportion of it is generally at most 20 moles, preferably less
than 10 moles, most preferably less than 5 moles per 100 moles of
the monomer used for the ring-opening polymerization.
The ring-opening polymerization of this invention may be
effectively carried out in the absence of an unsaturated polymer
but may further be carried out in the presence of an unsaturated
polymer.
The unsaturated polymer used for the purpose has a carbon-carbon
double bond in the polymer. Examples of the unsaturated polymers
are butadiene rubbers containing butadiene as the main component
(generally more than 50 % by weight), such as a butadiene
homopolymer rubber, a styrene-butadiene copolymer rubber, and an
acrylonitrile-butadiene copolymer rubber, chloroprene, rubbers,
isoprene rubbers, natural rubbers, ethylene propylene-diene
ter-polymers (generally called EPT or EPDM). Furthermore,
cycloolefinic rubber-like materials prepared by ring-opening
polymerizing cycloolefinic compounds may be used for the
purpose.
When the ring-opening polymerization of this invention is carried
out in the presence of the aforesaid unsaturated polymer, the
Mooney viscosity thereof is generally 10 - 200, preferably 20 -
150, more preferably 30 - 130. Also, it is preferred that the
unsaturated polymer has at least one carbon-carbon double bond,
more preferably more than 10 carbon-carbon double bonds per 1,000
total carbon-carbon bonds. This processes of producing these
unsaturated polymers and the properties thereof are described in
Kanbara et al; "Synthetic Rubber Handbook", 1967, published by
Asakura Shoten.
The unsaturated polymers used in this invention may be random
copolymer rubber-like materials or block copolymer rubber-like
materials as in case of, for example, styrene-butadiene copolymer
rubber-like materials.
In the case of carrying out the ring-opening polymerization of this
invention in the presence of the unsaturated polymer, the
proportion of the unsaturated polymer is generally at most 1,000
parts by weight, preferably less than 500 parts by weight, more
preferably less than 300 parts by weight per 100 parts by weigh of
the monomer used. If the proportion of the unsaturated polymer is
more than 1000 parts by weight per 100 parts by weight of the
monomer, a polymerized product showing the excellent properties is
not obtained.
In the practice of the ring-opening polymerization of this
invention in the presence of the unsaturated polymer, the polymer
is used as a solution or suspension (dispersion) thereof in the
monomer or a mixture of the monomer and the aforesaid inert organic
solvent. Furthermore, the ring-opening polymerization may be block
polymerization, graft polymerization, or a combination of graft
polymerization and block polymerization.
The graft or block polymerization product obtained by practicing
the ring-opening polymerization of this invention in the presence
of the unsaturated polymer is excellent in impact resistance as
compared with the ring-opening polymerization product obtained by
practicing the ring-opening polymerization of this invention in the
absence of the unsaturated polymer, although the extent of the
improved impact resistance may differ with different proportions of
the unsaturated polymer employed and thus is particularly useful in
the field in which high impact resistance is required.
After the ring-opening polymerization is over, the polymer obtained
can be recovered by various manners. In an example of the
recovering processes, the catalyst removal method and polymer
recovery method which are usually employed in the solution
polymerization of isoprene or butadiene may be applied. For
example, there is a process in which a solution containing the
ring-opening polymerization product, the unreacted monomer and the
catalyst is added to a lower alcohol (e.g., methanol and ethanol)
or the alcohol containing a small amount of hydrochloric acid,
whereby the catalyst is removed and at the same time the
ring-opening polymerization product obtained is precipitated and a
process in which an organic solvent solution containing the
ring-opening polymerization product, the unreacted monomer, and the
catalyst is uniformly mixed with an inert organic solvent (e.g.,
methylene chloride) which is immiscible with water, the resultant
mixture is treated with water containing a chelating agent (e.g.,
ethylene-diamine tetraacetic acid and nitrilotriacetic acid) and,
after removing the catalyst, the organic solvent is removed from
the reaction mixture. Other purification processes
(post-treatments) which can be employed for recovering the
ring-opening polymerization products of this invention are
described in the specifications of Japanese Patent Application Laid
Open Nos. 100,500/'73; 67,999/'74; 77,999/'75; 130,500/'74; and
Japanese Patent Application Nos. 119,968/'73; 123,329/'73 9208/'74;
68,680/'74; 61,851/'74; 69,243/'74; and 125,981/'74.
As mentioned above, in the case of producing the ring-opening
polymerization products having excellent physical properties (e.g.,
impact resistance and low-temperature impact resistance) and other
excellent properties such as moldability and transparency, the
ring-opening polymerization products having high adhesive property,
or the ring-opening polymerization products useful as ion-exchange
resins or coagulating agents according to the process of this
invention, the yield for the ring-opening polymerization product
per unit amount of catalyst is high owing to the quite high
polymerization activity. Thus, since a comparatively small amount
of catalyst can be used for producing a definite amount of a
ring-opening polymerization product, the amount of the catalyst can
be reduced as well as the ring-opening polymerization product
obtained can be quite easily purified or as the case may be, the
purification of the product may be omitted. Furthermore, according
to this invention, the ring-opening polymerization products (graft
and/or block polymerization products) having more excellent impact
resistance and low-temperature impact resistance can be obtained by
carrying out the ring-opening polymerization (graft and/or block
polymerization) in the presence of the unsaturated polymer.
Since the ring-opening polymerization products obtained by the
process of this invention have excellent properties as mentioned
above, they may be used as they are for various purposes but they
may be blended, according to the purposes, with one or more
additives having compatibility with the ring-opening polymerization
products or ring-opening graft and/or block polymerization
products, such as vinyl chloride polymers; a styrene homopolymer;
copolymers obtained by copolymerizing at least two monomers of
styrene, acrylonitrile, and methyl methacrylate; graft polymers
obtained by graft polymerizing at least one of styrene,
acrylonitrile, vinyl chloride, and methyl methacrylate to the
rubber-like material as shown below; butadiene rubbers containing
butadiene as the main component; chlorinated polyethylenic
rubber-like materials; acrylate rubber-like materials;
ethylene-vinyl acetate copolymer rubber-like materials; and
chloroprene rubbers. Moreover, the properties of the ring-opening
polymerization products or the ring-opening graft and/or block
polymerization products produced by the process of this invention
can further be improved by adding thereto additives generally used
for improving the properties of synthetic resins, such as
stabilizers to light (ultraviolet rays), heat, oxygen, and ozone; a
flame retarder; a lubricant; a filler; a reinforcing agent; an
impact resistance improving agent (e.g., a metal salt of a
carboxylic acid); a coloring agent; an antistatic agent; and a
foaming agent.
The ring-opening polymerization products, the ring-opening graft
and/or block polymerization products, and the aforesaid blends of
these polymerization products obtained in this invention may be
utilized as is and may also be molded into various forms such as
pellets, films, sheets, pipes, rods, containers. etc., by applying
thereto a molding method generally employed for synthetic resins,
such as a compression molding method, an extrusion molding method,
an injection molding method, and a blow molding method.
Also, the aforesaid ring-opening polymerization products, the
ring-opening graft and/or block polymerization products, or the
blends of them can be utilized as graft polymers by graft
polymerizing thereto a vinyl compound such as styrene, vinyl
chloride, acrylonitrile, and methyl methyacrylate or further they
may be subjected to a reaction for increasing the molecular weight
thereof.
Since, as mentioned above, the ring-opening polymerization products
and the like obtained by the process of this invention have various
merits and can be molded into various forms by employing the
aforesaid molding method, they can be used in various fields, such
as, for example, containers such as a bottle; films and secondary
fabrication products thereof (e.g., bags and packaging materials);
daily necessaries; machine parts; parts for electric equipment and
illuminators; pipes; and agricultural devices and parts
thereof.
Furthermore, the ring-opening polymerization products and the
ring-opening graft and/or block polymerization products obtained by
the process of this invention can be used, as is or after
increasing the molecular weight, as ion-exchange resins,
coagulating agents, adhesives, and coating materials.
The the invention will further be explained more in detail by the
following examples. In addition, in the examples and comparative
examples, the reduced viscosity was measured at a temperature of
30.degree. C. and at a concentration of 0.1 g/dl. using
dimethylformamide or 1,2-dichloroethane as the solvent.
EXAMPLE 1
Into a 500 milliliter three-necked flask, the inside of which was
completely replaced with nitrogen, were charged 35.1 g (0.152 mole)
of tungsten trioxide, 37.9 g (0.182 mole) of phosphorus
pentachloride, and 100 ml. of o-dichlorobenzene and after raising
the temperature of the reaction system to 120.degree. C., the
reaction was carried out for 30 minutes at the temperature while
vigoruously stirring the reaction system. The solution portion (the
supernatant liquid charged from colorless to deep red and in this
case a considerable amount of yellow precipitate was left at the
bottom of the flask. The concentration of tungsten in the solution
portion was confirmed to be 0.40 mole/liter by a fluorescent X-ray
measurement.
Then, in a one liter glass autoclave, the inside of which was
completely replaced with nitrogen, were placed 1.0 ml. (0.40
millimole as metallic tungsten) of the supernatant liquid of the
reaction product (the reaction product of tungsten trioxide and
phosphorus pentachloride), 250 ml. of 1,2-dichloroethane (prepared
by predrying a high-grade commercially available product over
calcium hydride and then rectifying it, the rectified product
contained about 5-7 ppm. of water, the product was also used in the
examples), 150 g. of 5-cyano-bicyclo [2,2,1]-heptene-2 (higher than
99.9% purity measured by gas chromatography, contained 60% endo
type) as the monomer, and 6.0 ml. of a 1,2-dichloroethane solution
of 1.0 mole/liter of diethylaluminum chloride and then the
polymerization was carried out for 60 minutes at 70.degree. C.
while stirring well.
After the polymerization was over, the polymerization system was
allowed to cool to about room temperature and after adding 150 ml.
of the aforesaid 1,2-dichloroethane, insoluble matters were
filtered away using a glass filter. To the filtrate was added 0.5
g. of bis(2-hydroxy-3-tert-butyl-5-methylphenyl)methane and the
mixture was poured into an amount of methanol of five times the
amount of 1,2-dichloroethane to precipitate the polymer formed. The
polymer was recovered by filtration, washed well with methanol, and
then dried overnight at 50.degree. C. under a reduced pressure,
whereby 78 g of a faint-yellow polymer was obtained. The
polymerization activity was 1,060 (g/g-w.hr) and the reduced
viscosity (solvent: dimethylformamide) of the polymer was 1.43.
EXAMPLE 2
The reaction product of the oxide and phosphorus pentachloride was
prepared by carrying out the reaction as in Example 1 for 60
minutes at room temperature with stirring, except for using, 21.9
g. (0.152 mole) of molybdenum trioxide in place of tungsten
trioxide. The color of the supernatant liquid changed to red purple
and a considerable amount of white precipitate was left at the
bottom of the flask. The concentration of molybdenum in the
supernatant was confirmed to be 0.38 g./liter by a fluoresent X-ray
measurement.
The same polymerization procedure as in Example 1 was followed
using, however, 2.0 ml. (0.76 millmole as metallic molybdenum) of
the supernatant liquid of the reaction product prepared in the
above step in place of the reaction product used in Example 1.
After the polymerization was over, the polymer formed gas recovered
(post-treatment) as in Example 1. Thus, 68 g. of a faint-yellow
polymer was obtained. The polymerization activity was 933
(g/g-Mo.hr) and the reduced viscosity of the polymer (solvent:
dimethylformamide) was 1.09.
COMPARATIVE EXAMPLE 1
The same polymerization procedure and post-treatment as in Example
1 were followed except that phosphorus petachloride was not used in
producing the reaction product, but no polymer was obtained.
COMPARATIVE EXAMPLE 2
The same polymerization procedure and post-treatment as in Example
1 were followed except that 93 mg. (0.40 millimole) of tungsten
trioxide and 100 ml. (0.48 millimole) of phosphorus pentachloride
were each separately added into the autoclave in place of the
supernatant of the reaction product of tungsten trioxide and
phosphorus pentachloride used as a catalyst component in Example 1.
Thus, 12 g. of polymer was obtained. The polymerization activity
was 163 (g/g-w.hr).
EXAMPLE 3
The same polymerization procedure as in Example 1 was followed
except that another organometallic compound as shown in Table 1 was
used in place of diethylaluminum chloride used in the
polymerization in Example 1 and also the polymerization temperature
as shown in Table 1 was employed. After the polymerization was
over, the polymer formed was recovered in each case. The
polymerization activity and the reduced viscosity (solvent:
dimethylformamide) of the polymer are also shown in Table 1.
Table 1
__________________________________________________________________________
Polymeri- Polymerization zation temp. Organometallic.sup.1)
activity Reduced No. (.degree. C) compound (g/g-w.hr) viscosity
__________________________________________________________________________
1 50 Triethylaluminum 978 1.20 2 80 Ethylaluminum 876 0.90
sesquichloride 3 50 Al(C.sub.2 H.sub.5).sub.3 /H.sub.2 O.sup.2) 917
1.17 4 60 (CH.sub.3).sub.3 SiOAl (C.sub.2 H.sub.5).sub.2.sup.3) 876
1.05 5 70 (C.sub.2 H.sub.5).sub.2 NAl(C.sub.2 H.sub.5).sub.2 795
0.98 6 70 Diethylzinc 889 1.11 7 70 Tetraethyltin 805 1.05 8 70
Diethylmagnesium 766 1.01
__________________________________________________________________________
1): Mole number same as in Example 1 as the concentration of metal
atom. 2): The reaction product of 2 moles of triethylaluminum and 1
mole of water, 3): The reaction product of 1 mole of trimethyl
silanole and 1 mole of triethylaluminum, 4): The reaction product
of 1 mole of diethylamine and 1 mole of triethylaluminum.
EXAMPLE 4
The same reaction procedure for producing the reaction product as
in Example 1 was followed except that the amount of phosphorus
pentachloride used in producing the reaction product in Example 1
was changed or the reaction component shown in Table 2 was used in
place of phosphorus pentachloride.
Then, the same polymerization procedure as in Example 1 was
followed except that the reaction product formed in the above step
was used in place of the reaction product used in Example 1. After
the polymerization was over, the polymer obtained was recovered as
in Example 1 in each case. In this case, the atomic equivalent of
metallic tungsten used was the same as in Example 1. The results
are also shown in Table 2.
Table 2
__________________________________________________________________________
Polymerization result
__________________________________________________________________________
Reaction component Amount (A) No. Kind (mole) (g) (B) (C)
__________________________________________________________________________
1 Phosphorus pentachloride 0.364 81 1,100 1.34 2 Phosphorus
pentabromide 0.500 74 999 0.98 3 Phosphorus pentafluoride 0.500 72
978 1.02 4 Phosphorus oxytrichloride 0.182 68 917 0.97 5* Aluminum
trichloride 0.182 42 571 1.18 6* Phosphorus trichloride 0.182 29
387 0.80
__________________________________________________________________________
*Comparative example (A): Yield, (B): Polymerization activity
(g/g-w.hr), (C): Reduced viscosity (solvent:
dimethylformamide).
EXAMPLE 5
The same polymerization procedure as in Example 1 was followed
except that after adding to the autoclave diethylaluminum chloride
used in the polymerization in Example 1, the molecular weight
controlling agent as shown in Table 3 was added in an amount of 1.0
mole% based on the amount of the monomer. After the polymerization
was over, the polymer formed was recovered as in Example 1 in each
case. The results are shown in Table 3.
Table 3 ______________________________________ Molecular weight
Polymerization Reduced No. controlling agent activity (g/g-w.hr)
viscosity.sup.1) ______________________________________ 1 Hexene-1
999 0.45 2 Butadiene 1,019 0.57
______________________________________ 1): Solvent
dimethylformamide.
EXAMPLE 6
The same polymerization procedure as in Example 1 was followed
except that the monomers shown in Table 4 were used in place of the
monomer used in Example 1. The polymer formed was recovered as in
Example 1 in each case. The results are shown in Table 4.
Table 4
__________________________________________________________________________
Polymerization activity Reduced No. Kind of monomer (g/g-w.hr)
viscosity.sup.1)
__________________________________________________________________________
1 5-Cyano-5-methyl-bicyclo[2,2,1]- 1,365 1.22.sup.a) heptene-2 2
5-Acetoxy-bicyclo[2,2,1]- 978 0.85.sup.a) heptene-2 3
5,6-Dimethoxycarbonyl-bicyclo- 1,039 0.70.sup.a) [2,2,1]-heptene-2
4 5-Methoxymethylbicyclo[2,2,1]- 978 0.69.sup.a) heptene-2 5
5-Chloromethyl-bicyclo[2,2,1]- 876 0.80.sup.b) heptene-2 6
5,5-Dichloro-bicyclo[2,2,1]- 815 1.11.sup.b) heptene-2 7
N-Phenyl-3,6-methylene-1,2,3,6- 1,182 1.05.sup.b)
tetrahydro-cis-phthalimide 8 2,3-Diethoxycarbonyl-bicyclo 1,264
1.17.sup.a) [2,2,1]-hepta-2,5-diene 9 N,N-Diethyl-bicyclo[2,2,1]-
937 0.94.sup.a) heptene-2-carbonamide-5 10
5-(4-Quinolyl)-bicyclo[2,2,1]- 998 0.81.sup.a) heptene-2 11
3,6-Methylene-1,2,3,6-tetrahydro- 1,283 0.97.sup.a) cis-phthalic
anhydride 12 N-Butyl-3,6-methylene-1,2,3,6- 1,121 1.07.sup.a)
tetrahydro-cis-phthalimide 13 5-(2-Pyridyl)-bicyclo[2,2,1]- 876
0.81.sup.a) heptene-2 14 1,4-Dihydro-1,4-methanonaphthalene 897
0.78.sup.b) 15 Cyclopentene.sup.2) 1,590 2.05.sup.b) 16
1,5-Cyclooctadiene.sup.2) 1,202 1.98.sup.b) 17
Bicyclo[2,2,1]-heptene-2.sup.2) 1,365 1.88.sup.b)
__________________________________________________________________________
.sup.1) a) Solvent dimethylformamide .sup.b) Solvent
1,2-dichloroethane .sup.2) Polymerized at 30.degree. C
EXAMPLE 7
The same procedure for producing the reaction product as in Example
1 was followed except that the oxides shown in Table 5-1 were used
in place of the tungsten trioxide used in the production of the
reaction product used in Example 1. Then, the same polymerization
procedure as in Example 1 was followed except that the reaction
product prepared in the above step was used in place of the
reaction product in Example 1. In this case, the atomic equivalent
of metallic tungsten or molybdenum in the supernatant liquid of the
reaction product was the same as that in Example 1. After the
polymerization was over, the polymer was recovered in each case.
The results are shown in Table 5-1.
Then, the same procedure for producing the reaction product as
mentioned above was followed except that phosphorus pentachloride
was not used. Then, the same polymerization procedure as described
above was followed. After the polymerization was over, the polymer
formed was recovered and the results are shown in Table 5-2.
Table 5-1 ______________________________________ Polymeri- zation
Oxide activity Amount (g/g-w or Reduced No. Kind (g) g-mo.hr)
viscosity.sup.1) ______________________________________ 1 Tungsten
dioxydi- chloride 40.5 1,019 1.40 2 Tungsten oxytetra- chloride
60.3 1,080 1.38 3 Molybdenum oxy- trichloride 45.0 836 1.12
______________________________________ .sup.1) Solvent
dimethylformamide
Table 5-2 ______________________________________ Polymeri- zation
Oxide activity Amount (g/g-w or Reduced No. Kind (g) g-mo.hr)
viscosity.sup.1) ______________________________________ 1 Tungsten
dioxytri chloride 40.5 0 -- 2 Tungsten oxytetra- chloride 60.3 0 --
3 Molybdenum oxy- trichloride 45.0 0 --
______________________________________ .sup.1) Solvent
dimethylformamide
COMPARATIVE EXAMPLE 3
The same procedure for producing the reaction product as in Example
1 was followed except that tungsten trioxide used for producing the
reaction product in Example 1 was not used. The same polymerization
procedure as in Example 1 was followed except that the reaction
product obtained in the above step was used. In this case, however,
no polymer was obtained.
COMPARATIVE EXAMPLE 4
The same polymerization procedure as in Example 1 was followed
except that the oxides shown in Table 6 were used in an amount of
0.40 millimole in place of the supernatant liquid of the reaction
product used in Example 1. After the polymerization was over, the
polymer was recovered in each case, the results being shown in
Table 6.
Table 6 ______________________________________ Polymerization
activity (g/g-w or Reduced No. Oxide g-Mo.hr) viscosity.sup.1)
______________________________________ 1 Tungsten trioxide 0 -- 2
Molybdenum trioxide 0 -- 3 Tungsten dioxydichloride 102 0.49 4
Tungsten oxytetrachloride 163 0.40 5 Molybdenum oxytrichloride 61
0.55 ______________________________________ .sup.1) Solvent
dimethylformamide
COMPARATIVE EXAMPLE 5
The same polymerization procedure as in Example 1 was followed
except that 2.0 ml. of a 1,2-dichloroethane solution of 0.2
mole/liter of tungsten hexachloride was used in place of the
supernatant liquid of the reaction product used in Example 1. After
the reaction was over, the polymer formed was recovered. The
polymerization activity was 713 (g/g-w.hr) and the reduced
viscosity of the polymer obtained was 1.21 (solvent
dimethylformamide).
COMPARATIVE EXAMPLE 6
The same polymerization procedure as in Comparative example 5 was
followed except that the organoaluminum chlorides shown in Table 7
were used in place of the diethylaluminum chloride used as the
organoaluminum compound in Comparative example 5. After the
polymerization was over, the polymer obtained was recovered in each
case. The results obtained are shown in Table 7.
Table 7 ______________________________________ Polymerization (A)
Organoaluminum activity Reduced No. (C.degree. ) compound.sup.1)
(g/g-w.hr) viscosity ______________________________________ 1 50
Triethylaluminum 571 0.98 2 80 Ethylaluminum sesqui- 442 0.70
chloride 3 50 Al(C.sub.2 H.sub.5).sub.3 /H.sub.2 O.sup.2) 407 1.09
4 60 (CH.sub.3).sub.3 SiOAl(C.sub.2 H.sub.5).sub.2.sup.3) 510 1.02
5 70 (C.sub.2 H.sub.5).sub.2 NAl(C.sub.2 H.sub.5).sub.2 428 0.89
______________________________________ (A)Polymerization
temperature, .sup.1) The same mole number as in Example 1 as the
concentration of aluminum. .sup.2) The reaction product of 2 moles
of triethylaluminum and 1 mole of water, .sup.3) The reaction
product of 1 mole of trimethylsilanole and 1 mole of
triethylaluminum, .sup.4) The reaction of 1 mole of diethylamine
and 1 mole of triethylaluminum.
EXAMPLE 8
The same polymerization procedure as in Example 1 was followed
except that 150 g. of a mixed solution of 70 mole% of
5-cyano-bicyclo-[2,2,1]-heptene-2 and 30 mole% of the monomer shown
in Table 8 was used in place of 5-cyano-bicyclo[2,2,1]-heptene-2 as
the monomer in Example 1. After the polymerization was over, the
polymer formed was recovered in each case. The results are shown in
Table 8.
Table 8 ______________________________________ Polymeri- zation
Copolymeriz- activity Reduced No. Monomer ation ratio.sup.1)
(g/g-w.hr) viscosity.sup.2) ______________________________________
1 Monomer (A).sup.3) 79 1,019 1.30.sup.a) 2 Monomer (B).sup.4) 77
978 1.09.sup.2) 3 Monomer (C).sup.5) 56 1,202 0.88.sup.b) 4 Monomer
(D).sup.6) 51 1,243 0.97.sup.b) 5 Monomer (E).sup.7) 78 978
1.00.sup.a) 6 Monomer (F).sup.8) 71 1,080 0.98.sup.b) 7 Monomer
(G).sup.9) 63 1,223 0.87.sup.b) 8 Monomer (G).sup.10) 75 1,182
1.08.sup.b) ______________________________________ .sup.1) The
copolymerization ratio of 5-cyan.-bicyclo[2,2,1]- heptene-2 i the
copolymer obtained, mole%. .sup.2) a) Solvent dimethylformamide
.sup.b) Solvent 1,2-dichloroethane .sup.3)
5-Cyano-5-methyl-bicyclo[2,2,1]-heptene-2, .sup.4)
5-Methyl-5-methoxycarbonyl-bicyclo[2,2,1]-heptene-2, .sup.5)
Bicyclo[2,2,1]-heptene-2, .sup.6) Cyclopentene, .sup.7)
5-(2-Pyridyl)-bicyclo[2,2,1]-heptene-2, .sup.8)
1,4-Dihydro-1,4-methanonaphthalene, .sup.9) 1,5-Cyclooctadiene,
.sup.10) 2,3-Diethoxycarbonyl-bicyclo[2,2,1]-hepta-2,5-diene
EXAMPLE 9
Into a one liter glass autoclave, the inside of which was
completely replaced with nitrogen, was charged 20.0 g. of
cis-1,4-polybutadiene, JSR BR-01 (trade name, made by Nippon
Synthetic Rubber Co., Mooney viscosity 45 (ML.sub.1+4, 100.degree.
C), cis-1,4 content 97.5%) which was reprecipitated from toluene
and methanol and dried overnight at about 60.degree. C. under a
reduced pressure and then 500 ml. of 1,2-dichloroethane was added
thereto followed by drawing to dissolve the polybutadiene
completely. The, to the solution thus prepared was added 30.0 g. of
5-cyano-bicyclo [2,2,1]-heptene-2 as the monomer followed by
stirring well and after adding thereto 5.0 ml. of the supernatant
liquid of the reaction product as used in Example 1 and 10.0 ml. of
a 1,2-dichloroethane solution of 1.0 mole/liter of diethylaluminum
chloride, the polymerization was carried out for 120 minutes at
70.degree. C with stirring.
After the polymerization was over, the polymer formed was recovered
as in Example 1. Thus, 48.0 g. of the polymer was obtained. When
the polymer was subjected to an infrared absorption spectrum
analysis, the characteristic absorption of
5-cyano-bicyclo[2,2,1]-heptene-2 and the characteristic absorption
of polybutadiene were observed. The polymer obtained was soluble in
toluene although the homopolymer of
5-cyano-bicyclo[2,2,1]-heptene-2 was insoluble in toluene.
Furthermore, when an extraction was tried using n-heptane which was
a solvent for polybutadiene, no extraction product was observed.
From the above facts, it was clear that the polymer obtained was
the copolymer of 5-cyano-bicyclo[2,2,1]-heptene-2 and polybutadiene
and the copolymer contained almost no polybutadiene homopolymer and
the ring-opening homopolymerization product of
5-cyano-bicyclo[2,2,1]-heptene-2.
EXAMPLE 10
The same polymerization procedure as in Example 1 was followed
except that after adding the reaction product used in carrying out
the polymerization in Example 1 to the reaction system, the
compound (as the third component for the catalyst) as shown in
Table 9 was added to the reaction system and, after stirring the
system vigorously for 10 minutes at room temperature,
1,2-dichloroethane was added to the reaction system. After the
polymerization was over, the polymer was recovered in each case.
The results are shown in Table 9.
Table 9 ______________________________________ Polymeri- zation
Third component for catalyst activity Reduced No. Kind
Amount.sup.1) (g/g-w.hr) viscosity.sup.2)
______________________________________ 1 Diethylacetal 2.40 1,590
1.07 2 Water 1.80 1,427 0.90 3 Isopropylamine 2.40 1,406 1.35 4
.alpha.-Chloroacetone 1.80 1,529 1.19 5 Triphenyl phosphine 3.60
1,610 1.00 6 Diethyl sulfide 4.80 1,549 0.88 7 Ethyl silicate 2.40
1,813 1.25 8 Ethyl silicate 4.80 1,793 1.29 9
Tris(.beta.-Chloro-ethyl) 4.80 1,945 1.20 phosphate 10
Tris(.beta.-Bromoethyl) 2.40 1,860 1.15 phosphate 11
Tris(2,3-dichloro-n- 4.80 1,977 1.16 propyl)phosphate
______________________________________ .sup.1) millimole .sup.2)
solvent dimethylformamide
COMPARATIVE EXAMPLE 7
The same polymerization procedure as in Example 10 - 9 was followed
except that 2.0 ml. of a 1,2-dichloroethane solution of 0.2
mole/liter of tungsten hexachloride was used in place of the
supernatant liquid of the reaction product used in Example 10 - 9.
After the reaction was over, the polymer formed was recovered. The
polymerization activity was 856 (g/g-w.hr) and the reduced
viscosity of the polymer obtained was 1.21 (solvent dimethyl
formamide).
EXAMPLE 11
The same procedure as that of producing the reaction product in
Example 1 was followed except that the reaction was carried out for
2.5 hours at 150.degree. C.
Then, in a one liter glass autoclave, the inside of which was
completely replaced with nitrogen, were placed 1.0 ml. (0.40
millimole as metallic tungsten) of the supernatant liquid of the
reaction product formed in the above step, 250 ml. of
1,2-dichloroethane and the kinds and amounts of the third
components for the catalyst as shown in Table 10, and then they
were vigorously stirred for 2 hours at the temperature as shown in
Table 10. Then, 150 g. of 5-cyano-bicyclo[2,2,1]-heptene-2 and 3.0
ml. of a toluene solution of 1.0 mole/liter of triisobutylaluminum
were added and then the polymerization was carried out for 60
minutes at 85.degree. C while stirring well.
After the polymerization was over, the polymer was recovered in
each case. The results are shown in Table 10.
Table 10 ______________________________________ Reaction
Polymerization Third component temperature activity No. Kind Amount
(g) (.degree. C) (g/g-w.hr) ______________________________________
1 .gamma.-A1.sub.2 O.sub.3 1.5 70 1,698 2 MgO 1.0 70 1,861 3
TiO.sub.2 " " 1,576 4 Cr.sub.2 O.sub.3 " " 1,616 5 V.sub.2 O.sub.5
" 150 1,657 6 MnO.sub.2 5.0 " 1,780 7 Fe.sub.2 O.sub.3 " " 1,739 8
CuO " " 1,685 9 Cd.sub.2 O.sub.3 " " 1,617 10 SiO.sub.2 0.5 100
1,848 11 Sb.sub.2 O.sub.3 " " 1,644 12 SeO.sub.2 " " 1,563 13
CeO.sub.2 " " 1,766 14 SiO.sub.2 -- 5.0 150 1,902 Al.sub.2 O.sub.3
15 -- -- 70 1,100 ______________________________________
EXAMPLE 12
The same polymerization procedure and post-treatment as in No. 1 of
Example 11 was followed except that the monomers shown in Table 11
were used in place of the monomer used in Example 11. The results
are shown in Table 11. The viscosity was measured by
dimethylformamide.
Table 11 ______________________________________ Polymeri- zation
activity Reduced No. Kind of monomer (g/g-w.hr) viscosity
______________________________________ 1 5-Methoxycarbonyl-bicyclo
1,875 1.32 [2,2,1]-heptene-2 2 5-Methoxy-bicyclo[2,2,1]- 1,630 1.20
heptene-2 3 N,N-Dimethyl-bicyclo[2,2,1]- 1,789 1.24
heptene-2-carbonamide-5 4 5-Chlor-bicyclo[2,2,1]- 1,617 1.18
heptene-2 5 3,6-Methylene-1,2,3,6-tetrahydro- 1,658 1.19
cis-phthalic anhydride 6 N-Methyl-3,6-methylene-1,2,3,6- 1,821 1.38
tetrahydro-cis-phthalimide 7 5-Phenyl-bicyclo[2,2,1]- 1,753 1.27
heptene-2 8 5-(2'-Pyridyl)-bicyclo[2,2,1]- 1,644 1.85 heptene-2 9
1,4-Hydroxy-1,4-methanonaphtha- 1,916 1.15 lene 10
2-Methoxycarbonyl-bicyclo[2,2,1]- 1,698 1.47 heptadiene-2,5 11
Cyclopentene 1,980 1.03 ______________________________________
EXAMPLE 13
The same procedure as that of producing the reaction product in
Example 1 was followed except that the reaction was carried out for
30 minutes at 150.degree. C.
Then, 1.0 ml. of the supernatant liquid of the reaction product
formed in the above step and the kinds and amounts of the third
components for the catalyst as shown in Table 12 were placed in a
one liter glass autoclave, the inside of which was completely
replaced with nitrogen, and then they were vigorously stirred for 5
hours at the temperatures as shown in Table 12. Then, 300 g. (2.5
moles) of 5-cyano-bicyclo[2,2,1]-heptene-2, 500 ml. of
1,2-dichloroethane and 6.0 ml. of a 1,2-dichloroethane solution of
1.0 mole/liter of diethylaluminum chloride were added and then the
polymerization was carried out for 60 minutes at 85.degree. C.
After the polymerization was over, the polymer was recovered in
each case. The results are shown in Table 12.
Table 12 ______________________________________ Polymeri- Third
component Reaction zation Amount temperature activity No. Kind (g)
(.degree. C) (g/g-w.hr) ______________________________________ 1
Mg(OH).sub.2 1.0 70 3,261 2 Ti(OH).sub.4 " " 3,002 3 Mn(OH).sub.2 "
" 3,207 4 Fe(OH).sub.3 " " 2,826 5 Ni(OH).sub.2 " 100 3,125 6
Zn(OH).sub.2 5.0 " 2,948 7 Al(OH).sub.3 " " 2,717 8 CuCO.sub.3 .
Cu(OH).sub.2 " " 3,274 9 LiOH " " 2,663 10 Sn(OH).sub.4 0.5 140
2,649 11 Bi(OH).sub.3 " " 2,853 12 -- 0 70 1,793
______________________________________
EXAMPLE 14
The same polymerization procedure and post-treatment as in No. 1 of
Example 13 was followed except that the monomers shown in Table 13
were used in place of the monomer used in Example 13. The results
are shown in Table 13.
Table 13 ______________________________________ Polymeri- zation
activity Reduced No. Kind of monomer (g/g-w.hr) viscosity
______________________________________ 1
5-Methoxycarbonyl-bicyclo[2,2,1]- 3,573 1.07 Heptene-2 2
5-Methoxy-bicyclo[2,2,1]-Heptene- 3,492 1.04 2 3
N,N-Dimethyl-bicyclo[2,2,1]- 3,125 1.28 heptene-2-carbonamide-5 4
5-Chlor-bicyclo[2,2,1]-heptene-2 3,016 1.25 5
3,6-Methylene-1,2,3,6-tetrahydro- 3,220 1.37 cis-phthalic anhydride
6 N-Methyl-3,6-methylene-1,2,3,6- 3,478 1.13
tetrahydro-cis-phthalimide 7 5-phenyl-bicyclo[2,2,1-]-heptene-2
3,845 1.29 8 5-(2'-Pyridyl)-bicyclo[2,2,1]- 2,962 1.32 heptene-2 9
1,4-Hydroxy-1,4-methanonaphtha- 3,628 1.44 lene 10
2-Methoxycarbonyl-bicyclo[2,2,1]- 2,799 1.18 heptadiene-2,5 11
Cyclopentene 3,890 1.11 ______________________________________
EXAMPLE 15
The same procedure as that of producing the reaction product in
Example 1 was followed except that the reaction was carried out for
30 minutes at 150.degree. C.
Then, 1.0 ml. of the supernatant liquid of the reaction product
formed in the above step and the kinds and amounts of the third
components for the catalyst as shown in Table 14 were placed in a
one liter glass autoclave, the inside of which was completely
replaced with nitrogen, and then they were vigorously stirred for 2
hours at the temperature as shown in Table 14. Then, 400 g. (3.36
moles) of 5-cyano-bicyclo[2,2,1]-heptene-2, 500 ml. of
1,2-dichloroethane and 6.0 ml. of a 1,2-dichloroethane solution of
1.0 mole/liter of diethylaluminum chloride were added and then the
polymerization was carried out for 60 minutes at 85.degree. C.
After the polymerization was over, the polymer was recovered in
each case. The results as shown in Table 14.
Table 14 ______________________________________ Reaction
Polymerization Third component temperature activity No. Kind Amount
(g) (.degree. C) (g/g-w.hr) ______________________________________
1 MgCl.sub.2 1.0 75 3,845 2 AlCl.sub.3 " " 4,212 3 LiCl " " 3,274 4
CuCl.sub.2 " " 4,035 5 ZnCl.sub.2 " " 3,573 6 CeF.sub.3 5.0 " 2,935
7 AlF.sub.3 " " 4,103 8 TiCl.sub.3 2.0 " 3,913 9 SnCl.sub.2 " 50
3,533 10 VOCl.sub.3 " " 3,872 11 Mg(OH)Cl 1.0 " 4,334 12 SbCl.sub.3
" " 3,424 13 CrCl.sub.6 " " 3,723 14 TeCl.sub.4 " " 3,804 15
MnCl.sub.2 " 30 3,003 16 -- -- -- 2,210
______________________________________
EXAMPLE 16
The same polymerization procedure and post-treatment as in No. 1 of
Example 15 was followed except that the monomers shown in Table 15
were used in place of the monomer used in Example 15.
Table 15 ______________________________________ Polymer- ization
activity Reduced No. Kind of monomer (g/g-w.hr) viscosity
______________________________________ 1 5-Methoxycarbonyl-bicyclo
4,022 1.29 [2,2,1]-heptene-2 2 5-Methoxy-bicyclo[2,2,1]- 4,348 1.35
heptene-2 3 N,N-Dimethyl-bicyclo[2,2,1]- 3,628 1.41
heptene-2-carbonamide-5 4 5-Chlor-bicyclo[2,2,1]-heptene-2 3,451
1.47 5 3,6-Methylene-1,2,3,6-tetrahydro- 3,832 1.38 cis-phthalic
anhydride 6 N-Methyl-3,6-methylene-1,2,3,6- 3,981 1.40
tetrahydro-cis-phthalimide 7 5-Phenyl-bicyclo[2,2,1]-heptene-2
4,321 1.09 8 5-(2'-Pyridyl)-bicyclo[2,2,1]- 3,668 1.21 heptene-2 9
1,4-Hydroxy-1,4-methanonaphtha- 3,315 1.53 lene 10
2-Methoxycarbonyl-bicyclo[2,2,1]- 3,546 1.20 heptadiene-2,5 11
Cyclopentene 4,420 1.15 ______________________________________
EXAMPLE 17
The same procedure as that of producing the reaction product in
Example 1 was followed except that the reaction was carried out for
2.5 hours at 150.degree. C.
Then, 1.0 ml of the supernatant liquid of the reaction product
formed in the above step and the kinds and amounts of the third
components for the catalyst as shown in Table 16 were placed in a
one liter glass autoclave, the inside of which was completely
replaced with nitrogen, and then they were vigorously stirred at
the temperature as shown in Table 16. Then, 400 g. of
5-cyanobicyclo[2,2,1]-heptene-2, 500 ml. of 1,2-dichloroethane and
3.0 ml of a toluene solution of 1.0 mole/liter of
triisobutylaluminum were added and then the polymerization was
carried out for 60 minutes at 85.degree. C.
After the polymerization was over, the polymer was recovered in
each case. The results as shown in Table 16.
Table 16 ______________________________________ Reaction Polymer-
Third component temper- ization Amount ature activity No. Kind (g)
(.degree. C) (g/g-w.hr) ______________________________________ 1
Ethylene diamine.Mg 1.0 75 3,777 2 " 5.0 " 3,628 3 Ethylene diamine
. Fe(II) 1.0 "3,261 4 Triethylene tetramine . Mn(II) " " 3,899 5
.alpha.,.alpha.'-Dipyridyl . " " 3,967 Fe(II) 6 Citric acid . " "
3,546 Cu(II) 7 Pyrophosphoric acid . Cu(II) " " 3,614 8 Salicyl
aldehyde . Zn(II) 2.0 60 3,981 9 8-Oxyquinoline . " " 3,288 Cd(II)
10 Elio black T . Mg(II) " " 3,438 11 Nitroacetic acid . Be(II) " "
3,913 12 Sodium ethylene dia- mine tetra-acetic acid " " 3,668 . Co
13 Nitroacetic acid . Al(III) 5.0 30 3,601 14 Ammonium triacetic
acid . Cr " " 3,274 15 Acetyl acetonate . Ti(IV) " " 3,016 16 -- --
1,725 ______________________________________
EXAMPLE 18
The same polymerization procedure and post-treatment as in No. 1 of
Example 17 was followed except that the monomers shown in Table 17
were used in place of the monomer used in Example 17. The results
are shown in Table 17.
Table 17 ______________________________________ Polymer- ization
activity Reduced No. Kind of monomer (g/g-w.hr) viscosity
______________________________________ 1 5-Methoxycarbonyl-bicyclo
3,764 1.49 [2,2,1]-heptene-2 2 5-Methoxy-bicyclo[2,2,1]- 4,130 1.37
heptene-2 3 N,N-Dimethyl-bicyclo[2,2,1]- 4,293 1.28
heptene-2-carbonamide-5 4 5-Chlor-bicyclo[2,2,1]-heptene-2 3,274
1.36 5 3,6-Methylene-1,2,3,6-tetrahydro- 3,424 1.33 cis-phthalic
anhydride 6 N-Methyl-3,6-methylene-1,2,3,6- 3,927 1.44
tetrahydro-cis-phthalimide 7 5-Phenyl-bicyclo[2,2,1]-heptene-2
4,116 1.41 8 5-(2'-Pyridyl)-bicyclo[2,2,1]- 4,307 1.20 heptene-2 9
1,4-Hydroxy-1,4-methanonaphtha- 3,560 1.30 lene 10
2-Methoxycarbonyl-bicyclo[2,2,1]- 3,261 1.25 heptadiene-2,5 11
Cyclopentene 4,440 1.18 ______________________________________
EXAMPLE 19
The same procedure as that of producing the reaction product in
Example 1 was followed except that the reaction was carried out for
60 minutes at 150.degree. C.
Then, 1.0 ml. of the supernatant liquid of the reaction product
formed in the above step and the kinds and amounts of the third
components for the catalyst as shown in Table 18 were placed in a
one liter glass autoclave, the inside of which was completely
replaced with nitrogen, and then they were vigorously stirred for 4
hours at the temperature as shown in Table 18. Then, 300 g. of
5-cyano-bicyclo[2,2,1]-heptene-2, 500 ml. of 1,2-dichloroethane and
6.0 ml. of a 1,2-dichloroethane solution of 1.0 mole/liter of
diethylaluminum chloride were added and then the polymerization was
carried out for 60 minutes at 75.degree. c.
After the polymerization was over, the polymer was recovered in
each case. The results are shown in Table 18.
Table 18 ______________________________________ Reaction
Polymerization Third component temp. activity No. Kind Amount (g)
(.degree. C) (g/g-w.hr) ______________________________________ 1
Mg(OC.sub.2 H.sub.5) 1.0 70 3,057 2 " 5.0 75 3,261 3 Li(OiC.sub.3
H.sub.7) 1.0 " 2,812 4 Ba(OC.sub.2 H.sub.5).sub.2 " " 2,976 5
Zn(OC.sub.2 H.sub.5).sub.2 " " 3,179 6 Mg(OC.sub.2 H.sub.5)Cl " "
3,057 7 B(Oi . C.sub.3 H.sub.7).sub.3 " " 2,690 8 Al(Oi . C.sub.3
H.sub.7).sub.3 0.5 80 2,514 9 Ga(OCH.sub.3).sub.3 " " 2,609 10
Si(OC.sub.2 H.sub.5).sub.4 " " 2,989 11 Ti(OiC.sub.3 H.sub.7).sub.4
" " 2,894 12 Zr(OC.sub.2 H.sub.5).sub.3 Cl " " 2,840 13
Mg(OPh).sub.2 2.0 60 2,544 14 Na(OC.sub.2 H.sub.5) " " 2,595 15
V(OC.sub.2 H.sub.5).sub.3 " " 2,513 16 W(OC.sub.3 H.sub.7).sub. 6
1.0 75 2,860 17 Mn(OC.sub.2 H.sub.5).sub.2 " " 2,741 18 Fe(OC.sub.2
H.sub.5).sub.3 " " 2,798 19 -- -- -- 1,567
______________________________________
EXAMPLE 20
The same polymerization procedure and post-treatment as in No. 1 of
Example 19 was followed except that the monomers shown in Table 19
were used in place of the monomer used in Example 19. The results
are shown in Table 19.
Table 19 ______________________________________ Polmer- activity
Reduced No. Kind of monomer (g/g-w.hr) viscosity
______________________________________ 1 5-Methoxycarbonyl-bicyclo-
2,826 1.29 [2,2,1]-heptene-2 2 5-Methoxy-bicyclo[2,2,1]- 3,329 1.28
heptene-2 3 N,N-Dimethyl-bicyclo[2,2,1]- 3,582 1.48
heptene-2-carbonamide-5 4 5-Chlor-bicyclo[2,2,1]-heptene-2 2,717
1.30 5 3,6-Methylene-1,2,3,6-tetrahydro- 2,894 1.40 cis-phthalic
anhydride 6 N-Methyl-3,6-methylene-1,2,3,6- 3,189 1.25
tetrahydro-cis-phthalimide 7 5-Phenyl-bicyclo[2,2,1]-heptene-2
3,802 1.33 8 5-(2'-Pyridyl)-bicyclo[2,2,1]- 2,541 1.41 heptene-2 9
1,4-Hydroxy-1,4-methanonaphtha- 3,016 1.48 lene 10
2-Methoxycarbonyl-bicyclo[2,2,1]- 2,677 1.47 heptadiene-2,5 11
Cyclopentene 3,665 1.02 ______________________________________
EXAMPLE 21
The same procedure as that of producing the reaction product in
Example 1 was followed except that the reaction was carried out for
60 minutes at 150.degree. C.
Then, 1.0 ml. of the supernatant liquid of the reaction product
formed in the above step and the kinds and amounts of the third
components for the catalyst as shown in Table 20 were placed in a
one liter glass autoclave, the inside of which was completely
replaced with nitrogen, and then they were vigorously stirred for 2
hours at the temperature as shown in Table 20. Then, 300 g. of
5-cyano-bicyclo[2,2,1]-heptene-2, 500 ml. of 1,2-dichloroethane and
6.0 ml. of a 1,2-dichloroethane solution of 1.0 mole/liter of
diethylaluminum chloride were added and then the polymerization was
carried out for 60 minutes at 80.degree. C.
After the polymerization was over, the polymer was recovered in
each case. The results are shown in Table 20.
Table 20 ______________________________________ Third component
Reaction Polymerization Amount temp. activity No. Kind (g)
(.degree. C) (g/g-w.hr) ______________________________________ 1
MgSO.sub.4 2.0 75 3,181 2 " 5.0 " 2,964 3 Na.sub.3 PO.sub.4 2.0 "
2,732 4 CePO.sub.4 " " 3,059 5 TiOSO.sub.4 " " 2,583 6
Cr(NO.sub.3).sub.3 " " 2,529 7 Mn(H.sub.2 PO.sub.4).sub.2 1.0 80
2,719 8 (NH.sub.4).sub.2 Fe(SO.sub.4).sub.2 " " 2,977 9 AgSO.sub.3
" " 2,962 10 CuSCN " " 3,087 11 Hg(CN).sub.2 " " 2,610 12
Ba(NO.sub.2).sub.2 " " 2,515 13 NaAl(SO.sub.4).sub.2 " " 2,529 14
NiCO.sub.3 2.0 60 2,624 15 KHCO.sub.3 " " 2,950 16 SnSO.sub.4 " "
3,004 17 VOSO.sub.4 . xH.sub.2 O " " 2,787 18 MgHPO.sub.4 " " 2,624
19 K.sub.2 PHO.sub.3 " " 2,515 20 AgCN " " 2,529 21 Na.sub.2
S.sub.2 O.sub.3 " " 2,730
______________________________________
EXAMPLE 22
The same polymerization procedure and post-treatment as in No. 1 of
Example 21 was followed except that the monomers shown in Table 21
were used in place of the monomer used in Example 21. The results
are shown in Table 21.
Table 21 ______________________________________ Reduced Polymer-
viscosi- ization ty (dime- activity thyl for- No. Kind of monomer
(g/g-w.hr) mamide) ______________________________________ 1
5-Methoxycarbonyl-bicyclo 3,263 1.45 [2,2,1]-heptene-2 2
5-Methoxy-bicyclo[2,2,1]- 3,480 1.40 heptene-2 3
N,N-Dimethyl-bicyclo[2,2,1]- 3,140 1.36 heptene-2-carbonamide-5 4
5-Chlor-bicyclo[2,2,1]-heptene-2 2,800 1.42 5
3,6-Methylene-1,2,3,6-tetrahydro- 2,868 1.47 cis-phthalic anhydride
6 N-Methyl-3,6-methylene-1,2,3,6- 3,100 1.29
tetrahydro-cis-phthalimide 7 5-Phenyl-bicyclo[2,2,1]-heptene-2
3,494 1.36 8 5-(2'-Pyridyl)-bicyclo[2,2,1]- 2,991 1.40 heptene-2 9
1,4-Hydroxy-1,4-methanonaphtha- 3,317 1.46 lene 10
2-Methoxycarbonyl-bicyclo[2,2,1]- 2,719 1.45 heptadiene-2,5 11
Cyclopentene 3,570 1.20 ______________________________________
EXAMPLE 23
The same procedure as that of producing the reaction product in
Example 1 was followed except that the reaction was carried out for
2.5 hours at 150.degree. C.
Then, 1.0 ml. of the supernatant liquid of the reaction product
formed in the above step and the kinds and amounts of the polymers
containing an active group as shown Table 22 were placed in a one
liter glass autoclave, the inside of which was completely replaced
with nitrogen, and then they were vigorously stirred for 5 hours at
the temperature as shown in Table 22. Then, 300 g. of
5-cyano-bicyclo[2,2,1]-heptene-2, 500 ml. of 1,2-dichloroethane and
6.0 ml. of a 1,2-dichloroethane solution of 1.0 mole/liter of
diethylaluminum chloride were added and then the polymerization was
carried out for 60 minutes at 85.degree. C.
After the polymerization was over, the polymer was recovered in
each case. The results are shown in Table 22.
Table 22 ______________________________________ Polymer- Third
component Reaction ization Amount temp. activity No. Kind (g)
(.degree. C) (g/g-w.hr) ______________________________________ 1
Polyvinyl alcohol 1.0 70 3,436 (polymerization degree about 1,700)
2 " 5.0 " 3,265 3 Cellulose " 3,012 4 Polyvinyl acetate " 3,271
(polymerization degree about 1,800) 5 Nylon-6 85 3,160 (molecular
weight about 10,000) 6 Polyacrylic amide " 3,367 (polymerization
degree about 1,500) 7 Poly(V-vinyl pyrroli- 60 3,254 done)
molecular weight about 50,000) 8 Phenol-aldehyde resin " 3,113
(molecular weight about 800) 9 Poly(N-vinyl pyridine) 70 3,225
(molecular weight about 1,000) 10 Polyurea " 3,351 (polymerization
degree about 500) 11 Polyacrylic acid 70 3,194 (polymerization
degree about 1,000) 12 Polyester.sup.*1 " 3,280 13
Polysulfide.sup.*2 " 3,175 14 Polyisocyanate 80 3,169 (molecular
weight about 30,000) ______________________________________ .sup.*1
The trade name "Viron-200" manufactured by Toyo Boseki K.K. .sup.*2
The trade name "Hitacol" manufactured by Hitachi Kasei K.K.
EXAMPLE 24
The same polymerization procedure and post-treatment as in No. 1 of
Example 23 was followed except that the monomers shown in Table 23
were used in place of the monomer used in Example 23. The results
are shown in Table 23.
Table 23 ______________________________________ Reduced Polymer-
viscosi- ization ty (dime- activity thyl for- No. Kind of monomer
(g/g-w.hr) mamide ______________________________________ 1
5-Methoxycarbonyl-bicyclo 3,558 1.21 [2,2,1]-heptene-2 2
5-Methoxy-bicyclo[2,2,1]- 3,300 1.18 heptene-2 3
N,N-Dimethyl-bicyclo[2,2,1]- 3,056 1.31 heptene-2-carbonamide-5 4
5-Chlor-bicyclo[2,2,1]-heptene-2 3,368 1.19 5
3,6-Methylene-1,2,3,6-tetrahydro- 3,395 1.20 cis-phthalic anhydride
6 N-Methyl-3,6-methylene-1,2,3,6- 3,409 1.17
tetrahydro-cis-phthalimide 7 5-Phenyl-bicyclo[2,2,1]-heptene-2
3,639 1.25 8 5-(2'-Pyridyl)-bicyclo[2,2,1]- heptene-2 3,232 1.09 9
1,4-Hydroxy-1,4-methanonaphthalene 3,436 1.25 10
2-Methoxycarbonyl-bicyclo[2,2,1]- 3,085 1.33 heptadiene-2,5 11
Cyclopentene 3,687 1.21 ______________________________________
* * * * *